CA2221776A1

CA2221776A1 - Aminosilane salts and silanamides of carboxylic acids as corrosion inhibitors

Info

Publication number: CA2221776A1
Application number: CA002221776A
Authority: CA
Inventors: Andreas Kramer; Markus Frey; Adalbert Braig
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1995-06-29
Filing date: 1996-06-17
Publication date: 1997-01-16
Also published as: ES2133972T3; EP0835289A1; MX9710433A; CN1117825C; EA199800091A1; AU699265B2; CN1189849A; US5879436A; BR9609321A; DK0835289T3; EP0835289B1; WO1997001606A1; DE69602530D1; AU6356096A; KR19990028652A; TW428018B; JPH11508927A; SG43378A1; ATE180269T1; EA000794B1

Abstract

A description is given of salts and amides derived from (i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of formula (I), and (ii) an aminosilane of formula (V) in which the general symbols are as defined in claim 1 as corrosion inhibitors in coating compositions for protecting metallic surfaces.

Description

W O 97/01606 PcT/~lr5l~26f .~mino.sil~nP salts and .sil~n~mides of carboxYlic acids as corrosion inhibitors The present in~e~Qn rPlates to coating compositionC comrri.cing an organic film-formin~
binder, preferably a surface-coating m~tPri~l, and ~mino~ n~ salts and/or .cil~n~mides of c~l ~ /lic acids as corrosion inhihit )re, to the use thereof in coating compositions for protecting metallic sllrfar~s, and to novel ~minosil~nP~ salts of carbw~ylic aeids.

The use of alkali metal, alk~linP earth metal, transition metal, ammoninm and amine salts of carboxylic acids, and of tr~ncition metal comr~leYps of kPtoc~rbo~ylic acids, as corrosion inhibit-~r.c in aqueous systems is known and is ~es~ri~e-l for ç~ampl~, in US-A-4 909 987, EP-A-0 412 933, EP-A-0 496 555, EP-A-0 554 023 or EP-A-0 619 290.

GB-A-2 279 344 describes carrier-bound ketocarboxylic acids as corrosion inhihit~ in eoating compositions for protecting me.t~llic ~ r~-~çs.

US-A-3 773 607 discloses the preparation and use of ~ n~mi~lPs as eoupling agents for glass fibres.

It has now been found that ~mino.cil~n~ salts and/or .cil~n~mities of earboxylic acids suppress the oxidation of metals, çspeci~lly iron, and that at the same time they greatly improve the a~lhçcic~n of the coating to metal in paints as well. These compounds are therefore sllit~bl~o in eoating compositions and as corrosion inhihhl)rs as well as a~1h,o.eion promoters.

The present invention therefore provides coating compositions comprising a) an organic film-forrning binder and b) as corrosion inhibitor a) at least one salt and/or ,B) at least one amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer, or a carboxylic acid of the fortn~

R1- X~--C C COOH (I) R3 --R~_ n CA 0222l776 l997-ll-2l W 0 97/01606 PCT~EP96/02C00 in which Rl is hydrogen, Cl-C25aL~yl, C2-C25aLkyl i~ r ~I by o'Xygn ~)E sulfur; C2-C24al~enyl, C4-Clscycloalkyl which is un.eubstit~lted or substituted by Cl-C4aL~cyl and/or carboxyl;
Cs-cl5cyclo~lkpnyl which is ~ln.e-lbstitllf~Pd or s~lbstitllt~d by Cl-C4alkyl and/or carboxyl;
Cl3-C26polycycloaLkyl. C7-Cgphenylalkyl which is ~ P-d or s-lb~ d on the phenyl ring by Cl-C4alkyl; -COR6, a 5- or 6-membered heterocyclic ring which is ~ln.~ e.(l or substitutpd by Cl-C4alkyl, Cl-c4~lkoxy~ halogen or c&ll,o~yl; a 5- or 6-membered het~rocyclic ring which is benzo-fused and is unsubstitutP.d or substi~ted by Cl-C4aLkyl, Cl-C4aLoxy, halogen or carboxyl; or else Rl is a radical of the formula II, I~
or IV

R.1 R7 R13 R10~ (Rl2)~C S N~= N~>_ R~ R8 Rl4 ~ (m) ~v) R2, R3, R4 and R5 independently of one another are hydrogen, hydroxyl, Cl-Cl8aL~coxy, C2-Cl8alkoxy which is ~ lup~d by oxygen or sulfur; Cl-C25alkyl, C2-C25alkyl which is llu~d by o~ygen or sulfur; C2-C24alkenyl, Cs-Cl5cycloalkyl which is ~ ub.~ ed or ~ ed by Cl-C4alkyl; C5-ClscycloaLkenyl which is unsubstituted or ~ub~ilu~d by Cl-C4aLkyl; phenyl or naphthyl which is unsubstituted or substituted by Cl-C4alkyl;
CrCgphenylaLkyl which is une~lbstitllted or substituted on the phenyl nng by Cl-C4aLkyl;
C1O-CI2naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by Cl-C4alkyl; or are -COR6, with the proviso that, if one of the radicals R2, R3, R4 and Rs is hyd~ yl, the other radical attached to the same carbon atom is other than hydloxyl; or else R2 and R3 or R4 and R5, together with the carbon atom to which they are ~tt~hed form an un.eubsti~lted or Cl-C4a]kyl-sub~Liluled Cs-Cl2cycloaLkylidene ring, R6 is hydroxyl, Cl-Cl8aLkoxy, C2-Cl8aLkoxy which is interrupted by oxygen or sulfur; or ,R15 is --N ~ or--N~c) R7, R8, Rg, RlOand Rll independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, Cl-C2saLkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; Cl-C2shaloaL~tyl, Cl-CI8aL~oxy, C2-Cl8aLkoxy which is interrupted by oxygen or sulfur; Cl-ClgaLIcylthio, C2-C24aLIcenyl, Cs-ClscycloaL~cyl which is unsubstituted or snbstit~fed by ~ ; ''5-Clseyclo~yt w~iich is u~ L~ or substituted by Cl-C4aLkyl; phenyl or naphthyl which is ull~ub~LiLuL~d or ~ub~liLu~d by Cl-C4alkyl;
C7-CgphenylaLlcyl which is lln.cub.etihlt~.d or substit~ted on the phenyl ring by Cl-C4alkyl;
C10-Cl2naphthylalkyl which is un~uL.~IiluLed or ~ub~LiLuL~d on the naphLhyl ring system by Cl-C4a~yl; phenoxy or n~phtho~y which is un~b~ d or s~lbstit~lted by Cl-4alkyl;
CTCgphenylalkoxy which is unsubstituted or ~ s~ d on the phenyl ring by Cl-C4aLkyl; C10-Cl2naphthylalkoxy which is unsubstituted or ~ e~ on the naphthyl ring system by Cl-C4alkyl; or else the radicals Rg and Rg or the radicals Rg and Rlo or the radicals Rlo and Rll or the ra~ l.e R7 and Rll, together with the carbon atoms to which they are ~ h~d form an unsubstit1lted or Cl-C4alkyl-, halogen- or Cl-C4alkoxy-substi-tuted benzo ring, with the proviso that at least one of the radicals R7, R8, Rg, Rlo and R
is hydrogen, Rl2 is hy~v~yl, halogen, nitro, cyano, CF3, Cl-C25aLkyl, C2-C25aLkyl which is ulLc~lupL~d by oxygen or sulfur; Cl-C25h~lo~lkyl~ Cl-Cl8alkoxy, C2-Cl8alkoxy which is inle~lu~ted by o~gyen or sulfur; Cl-Cl8alkylthio or C2-C24aL~cenyl, Rl3 and Rl4 independently of one another are hydrogen, Cl-C25alkyl, Cl-Cl8aL1coxy or Y-(CH2)scoR6~
RlS and Rl6 independently of one another are hydrogen, Cl-C25aLkyl, C3-C25aLI~yl which is ..I~.,~Led by oxygen or sulfur; C2~24aL~enyl, C5-Cl5cycloalkyl which is un.eubstitnt~d or SubSLiLuLed by Cl-C4alkyl; phenyl or naphthyl which is ~ U~ od or substitllted by Cl-C4alkyl, Xl is a direct bond, oxygen, sulfur, / =~, Cl-Cl8a~ylene, C2-CI8aLkylene which is i.l~llu~ted by oxygen or sulfur; C2-Cl8aL~enylene, C2-Cl8alkynylene, C2-C20alkylidene, C7-C20phenylaLlcylidene or Cs-C8cycloaLkylene, with the proviso that, if m and n are 0, X
is other than oxygen and sulfur, Y is oxygen or ~Ra .
Ra is hydrogen or Cl-C8aLlcyl, m and n independently of one another are integers from 0 to 10, p is an integer from 0 to 4, s is an integer from I to 8, and ii) an aminosilane of the formula V

, CA 02221776 1997-ll-21 W O 97/01606 PCT~EP96/02600 R~7 / (R1~)b N--X2 S~ (V) R18 --a (R20)4 a- b in which Rl7 and Rl8 indepçnr~P.ntly of one another are hydrogen, Cl-C2salkyl, 2-hyd.o~Lrt;l1,yl, C3-C2saL~nyl which is i~ ulJ~d by oxygen or sulfur; C2-C24alkenyl or ~ (Rl~)b --X2 S~
(R20)4 b Rl9 is Cl-C2saLIryl, C2-C2saL~cyl which is ~ ul,led by oxygen or sulfur; hyd ~yl, Cl-Cl8alkoxy orC2-C24alkenyl, R20 is hydru~yl, Cl-C~8aLkoxy or C2-Cl8alkoxy which is i~t~ u~Led by oxygen or sulfur;
and, if a and b together are 1, three r~ R20 together are N(CH2CH20-)3, R2l is hydrogen or Cl-C8alkyl, X2 is Cl-Cl8aLkylene, C2-C20alkylidene, CTC20phenylal~ylidene, Cs-C8cycloalkylene, phenylene or napl.illylene which is lm~l1bstitllted or ~ led by Cl-C4alkyl; or is C4-Cl8aLkylene which is i~ lup~d by oxygen, sulfur or ~R21, with the proviso that never two nitrogen atoms are attached to the same carbon atom, ais 1 or2, and bis0, 1 or2.

~ yl having up to 25 carbon atoms is a br~nchPd or Imbr~n~hed radical such as, for çY~mplP, methyl, ethyl, propyl, isc,prupyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopelllyl, l-m~ yll~eilLyl, 1,3-dimethylbutyl, n-hexyl, l-methyl-hexyl, n-heptyl, isoheptyl, l, 1,3,3-tetramethylbutyl, l-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, l-methylundecyl, dodecyl, 1,1,3,3,5,5-hP~r~methylhexyl, tridecyl, tetradecyl, pentadecyl, hPY~tlPCyl~ heptadecyl, octadecyl, eicosyl or docosyl. One of the preferred meE~nin~ of Rl, R2, R3, R4, Rs, R7, R8, Rg, Rlo, Rll, Rl2, Rl3, Rl4, Rls~ Rl6, Rl7, Rl8 and Rlg is, for example, Cl-C22aLkyl, especially Cl-C20aLkyl, e.g. Cl-Cl8aLkyl. A particularly prefelred n~ ning of R2, R3, R4, R5, R7, R8, Rg, Rlo. Rll, Rl2, Rl3, Rl4, Rl5, Rl6, Rl7, Rl8 and Rlg is, for example, Cl-Cl6aLkyl, in particular Cl-Cl2aLkyl, e.g. Cl-C8alkyl. A
likewise particularly ~fel-~d m~ning of R2, R3, R4, Rs~ R7, Rs, Rs. Rlo, R11~12~R13 WO 97tO1606 PCTAEP96/02600 S

Rl4, Rls. Rl6~ Rl7, Rl8, Rls and R2l is, for eY~mI)1p~ Cl-C6alkyl, in particular Cl-C4aLkyl, e.g. methyl or ethyl.

Alkyl having 2 to 25 carbon atoms which is L~llul)~d by oxygen or sulfur can be i.,~llul)led one or more times and is for example CH3-0-CH2-, CH3-S-CHr, CH3-O-CH2CH2-O-CH2-, CH3-(aCH2CH2-)20-CH2-, CH3-(O-CH2CH2-)30-CH2- or CH3-(O-CH2CH2-)40-CH2-. A particularly pl~f~ d me~nin~ of Rl, R2, R3, R4, Rs~ R7, R8, Rg, Rlo, Rll, Rl2 and Rlg is, for example, C2-Cl8alkyl i~ ~led by oxygen or sulfur, in particular C4-C18allyl i.lle,l uyled by oxygen, e.g. C4-Cl2alkyl il~el,ul~d by oxygen.

Alkyl having 3 to 25 carbon atoms which is ill~llu~i~d by oxygen or sulfur can be ellu~ted one or more times and is~ for eY~mr)lP, CH3-O-CH2CH2-, CH3-S-CH2CH2-, CH3-O-CH2CH2-O-CH2CH2-,CH3-(O-CH2CH2-)20-CH2CH2-, CH3-(O-CH2CH2-)30-CH2CHz- or CH3-(O-CH2CH2-)40-CH2CH2-. Preferred radicals R15, R16, R17 and R18 are those in which the carbon atom ~tt~ch~P~l to the nitrogen atom is not ~tt~hp~l simultaneously to an ~(lrli*on~l oYygen atom or sulfur atom. A particularly pl~f~l~d me~nin~ of Rls, Rl6, Rl7 and Rl8 is, for çY~mrlP~ C3-Cl8alkyl which is ill~llul)ted by oxygen or sulfur, in p~r irul~r C3-Cl8aLkyl which is L~l~llul,led by oxygen, e.g. C3-CI2aLkyl which is ill~llu~led by oxygen.

Alkenyl having 2 to 24 carbon atoms is a hr~nrhPd or unhr~nrhPd radical such as, for eY~mrle, vinyl, prop~llyl, 2-butenyl, 3-butenyL isobutenyl, n-2,4-~e.nt~ P-nyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-oct~-iecçnyl or n~-octa-decenyl. A particularly plefell~d m~nin~ of Rl, R2, R3, R4, Rs, R7, Rs, Rs, Rlo, Rll, Rl2, Rls, Rl6, Rl7, Rl8 and Rlg is aLlcenyl having 3 to 18 carbon atoms, in particular 3 to 12 carbon atoms, e.g. 3 to 10 carbon atoms.

C4-C15CycloaLkyl, especially Cs-Clscycloallcyl, which is unsubstituted or ~ub~luL~d by C~ 4all~yl and/or carboxyl and which contains preferably 1 to 3, in particular 1 or 2, branched or unbranched aLkyl group radicals and/or 1 or 2 carboxyl groups, is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, 2-carboxycyclohexyl, 3-carboxycyclohexyl, methylcyclohexyl, dimethylcyclohexyl, tri-methylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. A
l)r~relled mP~ning of Rl is, for ~ mple~ the C4-C12cycloaLkyls which occur in n~r~hthe~ic acid [J. Bll~kingh~m, Dictionary of Organic Compounds, Vol. 4, page 4152, 5th Edition (1982)]. A particularly preferred meaning of R2, R3, R4, R5, R7, R8, Rg, Rlo, Rll, Rls and CA 0222l776 l997-ll-2l W O 97/01606 PCTi~l,r/~26~-Rl6 is C5-Cl2cycloaLkyl, in particular Cs-CgcycloaL~cyl, e.g. cyclohexyl.

C5-ClsCycloaL4enyl wh~c~. is lln~ stit-lte~ Qr subst1t~lt~ by Ci-C~alkyl and/or carboxyl and which preferably contains 1 to 3, in particular 1 or 2, br~nchP~d or ~-nhr~n~hPd aLkyl group radicals and/or 1 or 2 carboxyl groups, is, for elr~mrl~, cyclopenlellyl, methylcyclope-llellyl, dimethylcyclopentenyl, cyclohP~nyl, 2-carboxycycloh~PYPnyl, 3-carboxycyclohexenyl, 2-carboxy-4-methylcyclohP,YPnyl, methylcyclohexenyl, dimethylcycloheYPnyl~ trimethylcyclohexenyl, tert-butylcyclQhe~Pnyl, cyclohep~el.yL
cyclooctenyl or cyclododecenyl. It is preferably Cs-cl2cyclo~lkpnyl~ in particular Cs-C8cycloaLkenyl, e.g. cyclohexenyl.

Cl3-C26Polycycloalkyl is, for eY~mplP, the Cl3-C26polycycloalkyls which occur inn~I~hth~.n~c acid [J. Bllc~n~h~m, Dictionary of Organic Compounds, Vol. 4, page 4152, 5th Edition (1982)].

C~CgPhenylaLkyl which is unsubstituted or substitllt~d on the phenyl radical by Cl-C4aLkyl and which preferably cont~inc 1 to 3, in par~cular 1 or 2, br~n~hPd or mbr~nched aL~cyl group r~dic~lc is, for e~mplp~ benzyl, oc-methylbenzyl, a,a-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4methylbenzyl, 2,4dimethylbenzyl, 2,6-dimethylbenzyl or ~tert-butylbenzyl. Benzyl is pr~rell~d.
A S- or 6-membered heterocyclic ring which ic ~ b~ Pd or subctit~lted by Cl-C4alkyl, Cl-C'-4~lkoxy, halogen or carboxyl and which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched aLkyl or aLkoxy group radicals, and preferably 1 to 3, in particular 1 or 2, heteroatoms from the group consi~sting of nitrogen, oxygen and sulfur is, for ~r~mple~ thienyl, 2-methylthienyl, 3-chlorothienyl, 3-metho~ylhiellyl, tetrahydrofuranyl, furyl, pyrrolidinyl, l-methylpyrrolidinyl, pyrrolyl, thiazolyl, iso-thiazolyl, imid~70lyl, carboxyimidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyridyl, piperidinyl, morpholinyl, pyiazillyl, carboxypyrazinyl, piperazinyl, triazinyl or 2,6-dimethoxytriazonyl .

A S- or 6-membered heterocyclic ring which is unsubstituted or sllbstituted by Cl-C4alkyl, Cl-C4aLIcoxy, halogen or carboxy and is benzo-fused, which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched aL~cyl or alkoxy group radicals and preferably 1 to 3, in particular 1 or 2, heteroatoms from the group consisting of nitrogen, oxygen and sulfur is, for example, benzothiazolyl, 5-chlorobenzothiazolyl, s-methoxybenzothi~olyL

Wo 97/01606 PCTIEP96/02600 S-methyl~en7~thi~7olyl, bçn~f-imi~l~7olyl, benzooxazolyl, benzoisothiazolyl or benzothienyl.
.

Alkoxy having up to 18 carbon atoms is a br~n~ d or unbr~n~hPd radical such as, for e~mple, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hRY~lecyloxy or octadecyloxy. Cl-C12ALkoxy is preferred, m particular Cl-ClOalkoxy, e.g. Cl-C8alkoxy. A
particularly p.er~led mP~ning of R2, R3, R4, R5, R6, R7, R8, Rg, Rll, Rl2, Rl3, Rl4, Rlg and R20 is Cl-C6alkoxy, in particular Cl-~4alkoxy, e.g. methoxy or ethoxy.

C2-Cl8Alkoxy which is i~ lu~)~d by oxygen or sulfur is, for e~r~mrle, CH3-O-CH2CH20-.CH3-S-CH2CH20-,CH3-O-CH2CH2-O-CH2CH20-, CH3-S-CH2CH2-S-CH2CH20-,CH3-S-CH2CH2-O-CH2CH20-CH3-(O-CH2CH2-)2O-CH2CH2O-, CH3-(O-CH2CH2-)3O~H2CH2O- or CH3-(O-CH2CH2-)40-CH2CH20--Phenyl or naphthyl sl~bstinlt~d by Cl-C4alkyl, which preferably cont~in.~ 1 to 3, in particular 1 or 2, aLl~yl groups, is, for ç~mpl~, o-, m- or p-melllylphellyL 2,3-dimethylphe-nyl, 2,4-dimeLllylpllel,yl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,~dime~lyl~hel,yl, 3,5-dim~ylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1,6-dimell~yln~phthyl or 4-tert-buLylnapllLllyl.

C10-Cl2NaphthylaLkyl which is un~ub~LiluL~d or substituted on the naphthyl ring system by Cl-C4aL~yl and which preferably cont~ins 1 to 3, in particular 1 or 2, br~nf~h.od or unbranched aL~yl group rAtlic~lc is, for e~mrle, naphthylmethyl, a-meLhyllldphthyl-methyl, oc,oc-dimethylnaphthylmethyl, naphthylethyl, 2-methyl-1-naphthylmethyl, 3-methyl- 1 -naphthylmethyl, 4-methyl- 1 -naphthylmethyl, 2,4-dimethyl- 1 -naphthylmethyl, 2,6-dimethyl- 1 -naphthylmethyl or 4-tert-butyl- 1 -naphthylmethyl.

An unsubstituted or Cl-C4aL~cyl-substituted Cs-Cl2cycloalkylidene ring which preferably contains 1 to 3, in particular l or 2, branched or unbranched alkyl group ~lic~lc is, for example, cyclopentylidene, rnethylcyclopentylidene, dimethylcyclopentylidene, cyclo-hexylidene, methylcyclohexylidene, dimethylcyclohexylidene, tri~nethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene, cyclooctylidene, cyclodecylidene orcyclododecylidene. Preference is given to cyclohexylidene and tert-butylcyclohexylidene.

W O 97/01606 PCT~EW6/02600 _ ~ _ Halogen is chlor~ne, bromine or iodine, for ex~mrle, preferably ehlnr nç..

~ o~lkyl having up to 25 carbon atoms is a branched or unbranched radical such as, for ex~mrle, chloromethyl, chloroethyl, chlo,ol~lul,yl, chlorobutyl or 3-chloro-1-butyl. A
preferred mç~ning of R7, R8, Rg, Rlo, Rll and R~2 is, for P~r~ml~lP, Cl-Cl8h~10~1kyl, in par~icular C~-Cl2haloalkyl, e.g. Cl-C8h~10~1kyl.

Alkylthio having up to 18 carbon atoms is a branched or ~lnhr~n~hPd radical such as, for e~mrle, methylthio, ethylthio, p~ yl~hio, is(J~ yllhio, n-l)u~ylLllio, isobutylthio, pe,l~yl~~~o, iso~,clllyil~lio, hexylthio, heptylthio, octylthio, de-iyll~lio, tetr~(lecylthio, hP~ e~;yl~lio or octadecylthio. ALkylthio having 1 to 12 carbon atoms is pler~l-ed, in particular 1 to 8 carbon atoms, e.g. 1 to 6 carbon atoms.

Cl-4AL~cyl-~.ub~.liLu~d phenoxy or naphthoxy, which preferably con~;lls 1 to 3, in particular 1 or 2, alkyl groups, is for çx~mrlP o-, m- or p-methyll hPnQxy, 2,3-dimetnyl-phenoxy, 2,4-dimethylphenoxy, 2,5-dimethylrh~noxy, 2,6-dimethylrhPno~ry, 3,4-dimethylphenoxy, 3,5-dimethylphPn()xy, 2-methyl-6-ethylph~Pnoxy, 4-tert-butyl-phenoxy, 2-ethylphenoxy, 2,6-diethylphenoxy, l-methyln~phthoxy, 2-me~lyli~aphthoxy, ~methylnaphthoxy, 1,6-dimethylnaphthoxy or 4-tert-butylnaphthoxy.

~rC9Phenylalkoxy which is u~.ul,,.lilu~d or ~ 'o~ lP~l on the phenyl ring by Cl-C4aLkyl, and preferably contains 1 to 3, in particular 1 or 2, branched or unbranched aLIcyl group radicals, is for example benzyloxy, 2-phenylethoxy, 2-methylbenzyloxy, 3-methylbenzyloxy, 4-methylbenzyloxy, 2,4-dimethylbenzyloxy, 2,6-dimethylbenzyloxy or 4-tert-butylbenzyloxy. Benzyloxy is preferred.

C10-Cl2Naphthyla1koxy which is unsubstituted or substituted on the naphthyl ring system by Cl-C4aLkyl, and preferably contains 1 to 3, in particular 1 or 2, branched or unbranched alkyl group radicals, is for example naphthylmethoxy, naphthylethoxy, 2-methyl-l-naphtnylmethoxy, 3-me~yl- l-naphthylmethoxy, 4-methyl- l-napht'nylmethoxy, 2,4-dimethyl- 1 -naphthylmethoxy, 2,6-dimethyl- 1 -naphthylmethoxy or 4-tert-butyl-1 -naphthylmethoxy.

Cl-Cl8AL~ylene is a branched or unbranched radical such as, for example, methylene, ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptame~ylene, g octamethylene, ~l~c~methylene, dodecamethylene or ocf~dec~methylene. A preferredm~ning of Xl is, for e~mrl~, Cl-Cl2aLkylene, in parucular Cl-ClOalkylene, e.g.
C~ alkylene. A ~.~.r~"r~l me~ning of X2 is, for example~ C2-C1,alkylene, in particular C2-ClOalkylene, e.g. C2-C8aLkylene. An especially preferred m~nin~ of X2 is, formplP, C2-C6alkylene, in particular C2-C4aLkylene, e.g. propylene.

C2-Cl8Alkylene which is ihlLellul)led by oxygen or sulfur can be ~IL~llul~L~d one or more times and is for eY~ml 1~ -CH2-O-CH2-, -CH2-S~H2-, -CH2-NH-CH2-, -CH2-O-CH2CH2-O-CH2-,-CH2-(O-CH2CH2-)20-CHr,-CH2-(O-CH2CH2-)30-CH2-, -CH2-(O-CH2CH2-)40-CH2- or -CH2CH2-S-CH2CH2-. A ~l~r~ d m~nin~ of Xl is, for ç~m~le, C2-Cl8alkylene illLellupt~d by oxygen, in particular C4-Cl8alkylene inLel.u~d by oxygen, e.g. C4-Cl2aLkylene in~l,u~ted by oxygen.

C4-Cl8Alkylene ~--ui)ted by oxygen, sulfur or ~R2, can be interrupted one or more times and is for ç~ )l? -CH2CH2-NH-CH2CH2-, -CH2CH2-N(CH3)-CH2CH2-, -CH2CH2-NEI-CH2CH2CH2-,-CH2CH2-S-CH2CH2-,-CH2CH2-O-CH2CH2-O-CH2CH2-, -CH2CH2NH-CH2CH2-NH-CH2CH2CH2--CH2CHr(O-CH2CH2-)20-CH2CH2-, -CH2CH2-(O-CH2CH2-)3O-CH2CH2- or-CH2CH2-(O-CH2CH2-)4O-CH2CH2-. A
preferred meaning of X2 is, for example, C4-Cl2aLkylene in~ell upL~d by oxygen, sulfur or ~N R21, in particular C4-Cl2aLkylene intermpted by ~R2l, e.g. C4-Cl2alkylene illLt;llul,Led by ~H .

C2-Cl8AL~enylene is for e~mple vinylene, meLhylvillylelle, octenylethylene or dode-cenylethylene. C2-Cl2ALkenylene is ~,lefell~d, especially C2-~'8~lkPnylene. A particularly preferred m~nin~ of Xl is C2-C4~1k.onylene, e~peci~lly vinylene.

C2-Cl8ALcynylene is for example --C--C-- , 2-pl~pyl~ylene ( - C ~ C - CH2--), 2-butynylene (--CH2--C _ C - CH2-- ), 2-pentynylene, 2-hexynylene, 3-hexynylene,3-heptynylene, 2-decynylene, 4-decynylene or 8-octadecynylene. A preferred mç~nin,~ of Xl is C2-CI2aL~ynylene, in particular C2-C8aLkynylene, e.g. 2-butynylene.

Alkylidene having 2 to 20 carbon atoms is for example ethylidene, propylidene, buty-lidene, pen~lidene, 4-methylpel,lylidene, heptylidene, nonylidene, tridecylidene, nona-decylidene, 1-methylethylidene, l-ethylpropylidene or 1-ethylpentylidene. A preferred W O 97/01606 PCT~EP96/02600 m~nin~ of Xl and X2 is, for example, aL~cylidene having 2 to 16 carbon atoms, inparticular 2 to 12 carbon atoms, e.g. 2 to 8 carbon atoms.

Phenylall~ylidene having 7 to 20 carbon atoms is for çx~mple benzylidene, 2-phenyl-ethylidene or l-phenyl-2-hexylidene. A pl~Ç~.-ed me~ning of Xl and X2 is, for e~mple, phenylalkylidene having 7 to 16 carbon atoms, in particular 7 to 12 carbon atoms, e.g. 7 to 9 carbon atoms.

Cs-CgCycloalkylene is a s~ ~tecl hydrocarbon group having two free valences and at least one ring unit and is, for e~mple, cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene. Cyclohexylene is pl~rell~d.

Un~ub~ cl or C1-C4aLkyl-substihlted phenylene or naphthylene is for çx~mple 1,2-, 1,3-, 1,~phenylene, 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene. 1,4-Phenylene is ~l~fell~d.

The novel component (,B) is nn~erstQod to refer to amides of the fi~ VIa or VIb O
A--C\ ~(Rl9)b N X2--S~
N--X2 Sl R13 ( 20)4a- b ~o 20 4 -a - b -- --a -- --a (VIa) (VIb) in which A is R1 -- Xl C C or, for example, the polymeric part of R3R~;
-- --m -- --n polyacrylic acid.

Coating compositions to be mentioned in particular are those comprising as component (b) CA 0222l776 l997-ll-2l W O 97/01606 PcT/~ ~26oo a salt and/or an amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formul~ I and ii) an ~mino.cils~ne of the formula V in which Rl is C1-C25alkyl. C2-Cl8alkyl which is int~llui)led by oxygen or sulfur; C2-Cl8alkenyl, Cs-Cl2cycloaLkyl which is 1lnc~lbstihlted or substit~lt~d by Cl-C4alkyl and/or carboxyl;
C5-Cl2cyclo~lk~onyl which is u-l~ul)~lilul~d or substit~ltpcl Cl-C4alkyl and/or c~l,o~yl;
Cl3-C26polycycloalkyl, C7-CgphenylaL~cyl, -COR6 or a radical of the formula II, m or IV

R" R7 R13 R~o~ )~CS N
Rg R8 R14 (II) (m) (IV) R2, R3, R4 and Rs independently of one another are hydrogen, hydroxyl, Cl-Cl2alkoxy, CrCl2alkoxy which i~s i~ u~led by oxygen or sulfur; Cl-Cl8aLkyl, C2-Cl8aLkyl which is u~ d by oxygen or sulfur; C2-Cl8alkenyl, C5-Cl2cycloalkyl~ Cs-Cl2cycloalkenyl, phenyl, naphthyl, CrCgphenylalkyl, ClO-Cl2naphthylaLkyl or-COR6, with the proviso that, if one o~ the r~ 1.c R2, R3, R4 and Rs is hy~ yl, the other radical ~tt~ehP~l to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and Rs, together with the carbon atom to which they are attached, form a Cs-ClOcycloalkylidene ring, R6 is lly~v~yl, Cl-Cl2aLkoxy, C2-Cl2aLIcoxy which is i-~te~l upted by oxygen or sulfur; or ~ 15 is --N~ or--N~O, R7, R8, Rg, Rlo and Rl 1 independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, Cl-Cl8aLlcyl, C2-Cl8alkyl which is h~ u~ d by oxygen or sulfur; Cl-Cl8haloaLkyl, Cl-Cl2aLlcoxy, C2-Cl2aL~coxy which is interrupted by oxygen or sulfur; Cl-Cl2aLkylthio, C2-ClgaL~enyl, Cs-Cl2cycloalkyl, Cs-Cl2cycloaLkenyl, phenyl, naph~yl, CTCgphenylaLkyl, ClO-Cl2naphthylallcyl, phenoxy, naphthoxy, C7-Cgphenyl-aLkoxy or ClO-Cl2naphthylaLcoxy; or else the r~(iirSll~ R8 and Rg or the radicals Rg and R1o or the r~ c Rlo and Rll or the radicals R7 and Rll, together with the carbon atoms to which they are attached, form a benzo ring, with the proviso that at least one of the radicals R7, R8, Rg, Rlo and Rll is hydrogen, Rl2 is hydroxyl, chlorine, nitro, cyano, CF3, Cl-C18alkyl, C2-Cl8aLkyl which is interrupted W 0 97/01606 PcT/~s/~26oo by oxygen or sulfur; Cl-Cl8haloaLkyl, Cl-Cl2aLkoxy, C2-Cl2aLkoxy which is interrupted by oxygen or sulfur; Cl-Cl2alkylthio or C2-Cl8aLkenyl, Rl~ and ~14 i--~ p~ .h1~ltly of one anQ~ U~ hy~krQgen ~r~8 ~ 1-Cl-C12a~~XY or -Y-(CH2),jcOR6~
Rl5 and Rl6 indepe.ndlontly of one another are hydrogen, Cl-Cl8aLlcyl, C3-Cl8alkyl which is ellu~d by oxygen or sulfur; C2-Cl8alkenyl, Cs-Cl2cycloalkyl, phenyl or naphthyl,Rl7 and Rl8 indepenrlP-ntly of one another are hydrogen, Cl-Cl8aL~yl, C3-Cl8aLkyl which is i~llu~d by oxygen or sulfur; or is C2-Cl8aLlcenyl, Rlg is C1-Clgalkyl, C2-Cl8aLlcyl which is i~ lul~led by oxygen or sulfur; hy~'oAyl, Cl-Cl2aL~oxy or C: 2-Cl8aLkenyl, R20 is llydLuAyl, Cl-Cl2aLkoxy or CrCl2aLlcoxy which is inlellul~led by oxygen or sulfur;
and, if a and b together are 1, three r~dic~l.c R20 together are N(CH2CH20-)3, R2l is hydrogen or Cl-C6alkyl, Xl is a direct bond, oxygen, sulfur, ~C = O, Cl-Cl2alkylene, C2-Cl2alkylene which is ihlt~,~lupled by oxygen or sulfur; C2-Cl2aL~enylene, CrCl2alkynylene, C2-Cl6aLkylidene, C~C16phenylaLkylidene or Cs-C8cycloalkylene, with the proviso that, if m and n are 0, X
is other than oxygen and sulfur, X2 is C2-Cl2aLkylene, C2-Cl6alkylidene, C7-Cl6phenylaLI~ylidene, C5-C8cycloaLkylene, phenylene, naphthylene, or C4-Cl2aLlcylene which is i~ llupled by oxygen, sulfur or J~R21, with the proviso that never two nitrogen atoms are ~ h~od to the same carbon atom, Y is oxygen or ~Ra, Ra is hydrogen or Cl-C6aLkyl, m and n indepe.n~lently of one another are integers from O to 8, p is an integer from O to 2, and s is an integer from 1 to 6.

Coating compositions which are of interest are those comprising as component (b) a salt and/or an amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~mino.~ nP~ of the formula V in which Rl is Cl-C2saL~cyl, C2-Cl2aLkyl which is interrupted by oxygen; C2-CI8aLkenyl, C5-C12cycloaL~cyl, C5-Cl2cycloaL~enyl which is unsubstituted or substituted by C1-C4aLkyl and/or carboxyl; C7-CgphenylaLIcyl, -COR6 or a radical of the form~ II or III

~ R1~ ~ ~ N

R2, R3, R4 and Rs indepen~P.ntly of one another are hydrogen, Cl-~8~1koxy, Cl-Cl8aL~cyl, C2-Cl2alkyl which is i,~ luyled by oxygen; CrCl2alkenyl, Cs~8cycloalkyl, Cs-C8cyclo-aL~enyl, phenyl, naphthyl, benzyl or -COR6, or else R2 and R3 or R4 and Rs, together with the carbon atom to which they are attached, form a Cs-C7cycloalkylidene ring, R6 is hydlo~yl, Cl-Cl2alkoxy, C2-Cl2alkoxy which is in~luy~d by oxygen or sulfur; or ,R15 , ~ 16 R7, R8, Rg, Rlo and Rll indepçn-lently of one another are hydrogen, ~yd~ yl, çhln~in~, nitro, -COR6, Cl-Cl2alkyl, C2-Cl2aLkyl which is inlelluyled by oxygen; Cl-C8alkoxy, Cl-C8alkylthio, C2-Cl2aLl~enyl, Cs-C8cycloaLIcyl, Cs-C8cyclo~lkP-nyl, phenyl, naphthyl, benzyl, phenoxy, naphthoxy or benzyloxy; or else the r~rlic~l~ Rg and Rlo or the r~ic~l~
Rlo and Rll together with the carbon atoms to which they are ~tf~ch~.~ form a benzo ring, with the proviso that at least one of the r~ al~ R7, R8, Rg, Rlo and Rll is hydrogen, Rl2 is hyd~ yl, chl-7rinP., Cl-Cl2aLkyl, Cl-Cl2alkoxy, C2-Cl2alkoxy which is i~lluyled by oxygen, Rls and Rl6 independently of one another are hydrogen, Cl-Cl2alkyl, C2-Cl2alkenyl, Cs-C7cycloalkyl, phenyl or naphthyl, Xl is a direct bond, sulfur, / =~, Cl-Cl2aLkylene, C2-Cl2aLkylene which is i l~llulJ~d by oxygen; C2-Cl2alkenylene or C5-C8cycloalkylene, with the proviso that, if m and n are 0, Xl is other than sulfur, m and n independently of one another are integers from O to 8, and p is an integer from O to 2.

Preferred coating compositions are those compri.~in~ as component (b) a salt and/or an ~ amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an aminosilane of the formula V in which Rl is Cl-C2saLkyl, C2-Cl8alkenyl, C5-C8cycloaL~cyl, C5-C8cycloaLkenyl which is unsubstituted or sllhstit~t~d by Cl-C4aLkyl and/or carboxyl; benzyl, -COR~ or a radical of the formula II or m CA 0222l776 l997-ll-2l W O 97/01606 PCT~EP96/02600 Rll R7 (II) R10~ (R12)~C S

R2, R3, R4 and R5 independently of one another are hydrogen, Cl-Cl2aL~cyl, C2-Cl2alkenyl, cyclohexyl, phenyl, naphthyl, benzyl or-COR6, ~R15 R6 is hydroxyl, Cl-C8aLkoxy or --N~
R7 is hydrogen, chlorine or Cl-C4alkyl, R8 is hydrogen, hydroxyl, Cl-C4alkyl, nitro or chlorine, Rg is hydrogen or Cl-C4aLkyl, Rlo is hydrogen, Cl-C4aLkyl, nitro, chlorine or -COR6, Rll is hydrogen or Cl-C4alkyl, R12 iS chl~)rine~ Cl-C8alkyl or Cl-C8aLkoxy, Rls and Rl6 indepen~e.ntly of one another are hydrogen or Cl-C4alkyl, Xl is a direct bond, sulfur, /C = O or Cl-Cl0aL~ylene, with the proviso that, if m and n are 0, Xl is other than sulfur, m and n indepe~lently of one another are integers from 0 to 4, and p is 1.

Other preferred coating compositions are those Comllri.~ing as component (b) a salt and/or an amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~mino~ ne of the formula V in which Rl7 and Rlg independently of one another are hydrogen, Cl-Cl2alkyl, C3-Cl2aLkyl which is interrupted by oxygen; or C2-Cl2aL~enyl, Rlg is Cl-Cl2aL~cyl, C3-Cl2aL~cyl which is interrupted by oxygen; hydroxyl, Cl-Cl0aLkoxy or C2-Cl2aL~enyl, R20 is hydroxyl, Cl-Cl0aLkoxy or C2-Cl0aLkoxy which is interrupted by oxygen; and, if a and b together are 1, three radicals R20 together are N(CH2CH20-)3, R2l is hydrogen or Cl-C4aLkyl, X2 is C2-Cl0aLkylene, C2-Cl2allylidene, Cs-C8cycloaLkylene, phenylene, or C4-Cl2aLkylene which is interrupted by ~R21, with the proviso that never two nitrogen wo 97/0l606 PCTtEP96102600 atoms are attached to the same carbon atom.

A1SQ o~ in~erest are coa~ing somrQsitions comr)ri.cin~ as component (b) a salt and/or an amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~minosi1~ne of the formul~ V in which Rl7 and Rl8 independently of one another are hydrogen or Cl-C8alkyl, Rlg is Cl-C8alkyl, llydLo~yl, Cl-C8alkoxy or C2-C8aLkenyl, R20 is hydloAyl or Cl-C8aL~oxy; and, if a and b together are l, three r~di~ R20 together are N(cH2cH2O-)3~
R2l is hydrogen or Cl-C4alkyl, X2 is C2-C6aLkylene, C5-C8cycloaLkylene, phenylene, or C4-C8alkylene which is ul~led by ~R21, wi~ the proviso that never two nitrogen atoms are attached to the same carbon atom, a is l, and b is 0 or l.

Coating compositions of special interest are those co...l~. ;.ci,.g as component (b) a salt and/or an amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an aminosilane of the formula V in which Rl is Cl-C2saL~yl, C2-Cl6aL~cenyl, 2-carboxy~-methylcyclohexenyl, cyclohexyl, benzyl, -COR6 or a radical of the formula II or m (II) Rl~ F~N

R2, R3, R4 and Rs independently of one another are hydrogen, Cl-C8alkyl, phenyl, benzyl or -COR6, ~R~ ~;
R6 is hydroxyl, Cl-C4aL~coxy or --N~
R7 is hydrogen or Cl-C4aLkyl, R8 is hydrogen, hydroxyl, Cl-C4aLkyl, nitro or chlorine, Rg is hydrogen or Cl-C4aLkyl, Rlo is hydrogen, Cl-C4aLkyl, nitro, chlorine or -COR6, W O 97/01606 PCT~EP96/02600 Rll is hydrogen or Cl-C4aLkyl, R12 is chlorine, Cl-C4aLkyl or Cl-C4aLkoxy, Rl~; an~ Rl6 indepen-lently of one another are hydrogen or Cl-C4alkyl, Rl7 and Rl8 indepe.n-lently of one another are hydrogen or Cl-C4aLkyl, Rlg is Cl-C6aLkyl, C2-('6~1kP.nyl, hydroxyl or Cl-C4aLkoxy, R20 is hydro~-yl or Cl-C4aL~oxy, and, if a and b together are 1, three radicals R20 together are N(CH2CH20-)3~
R2l is hydrogen or Cl-C4aLkyl, Xl is a direct bond, sulfur, ~C = O or C1-ClOaLkylene, with the proviso that, if m and n are O, Xl is other than sulfur, X2 is C2-C6aL~cylene, cycloh~ylene, or C~-C8alkylene which is mLell~led by ~R21,with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1, bisOorl, m and n independently of one another are O, 1 or 2, and pisOorl.

C'o~ting compositions which are especially of particular interest are those compri.~ing as component (b) a salt andlor an amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~minosil~ne of the formula V in which Rl is Cl-Cl8alkyl, 2-carboxy-~methylcyclohexenyl, -COR6 or a radical of the formula II
or III

(II) Rlo~ (R12)~N

R0 Rs R2 is hydrogen, R3 is hydrogen or-COR6, R4 and R5 are hydrogen, R6 is hydroxyl, R7 is hydrogen, WO 97/01606 PCT/EPs6/02600 R8 is hydrogen, hydroxyl, C1-C4aLkyl, nitro or chlorine, Rg is hydrogen, Rlo is hydrogen, Cl-C4aLkyl or nitro, Rll is hydrogen, Rl7 and Rlg are hydrogen or methyl, Rlg is Cl-C4alkyl, hydl~Lyl or Cl-C4alkoxy, R20 is hy~oAyl or Cl-C4aL~oxy, and, if a and b together are 1, three r~(lic.~ R20 together are N(cH2cH2O-) R2l is hydrogen, Xl is a direct bond, sulfur, / = ~ or Cl-C8aLkylene with the proviso that, if m and n are ~, Xl is other than sulfur, X2 is C2-C4allylene, or C4-C6alkylene which is ih~ lu~ted by ~R21, with the proviso that never two nitrogen atoms are ~tt~chP.cl to the same carbon atom, ais 1, b is 0 or 1, m and n indepen~lently of one another are 0 or 1, and pisO.

.o~tingS of very particular interest are those in which component (~) is derived from an ~mino.~ n-o. of the formula V in which at least one of the r~ Rl7 and Rl8 is hydrogen.

Special pr~rel~nce is given to coating compositions c- mpri.cing as component (b) a salt and/or an amide derived from i) a polyacrylic acid, an acry-lic acid-maleic acid copolymer or a carboxylic acid of the formula I, wherein the carboxylic acid of the formula I is acetic acid, heptanoic acid, o-toluic acid (2-methylbenzoic acid), 2-ethylhexanoic acid, stearic acid, lauric acid, oleic acid, linoleic acid, acetylenecarboxylic acid, cycloh~.Y~n~c~rboxylic acid, naphthenic acid, benzoic acid, o-nitrobenzoic acid, p-nitrobenzoic acid, o-chlorobenzoic acid, 4-methyl~cyclohexen(~-1,2-dicarboxylic acid, 2-dodecenylsuccinic acid, phthalic acid, n~phthojc acid, phenylacetic acid, cinn~mic acid, sebacic acid, succinic acid 3-(4-methylbenzoyl)propionic acid, maleic acid, acetylen~.dic~rboxylic acid, cycloheY~nP-lic~rboxylic acid, trim~llitic acid, hydroxybutyric acid, m~ndelic acid, salicylic acid, llydl~yllaphthoic acid, hydroxysuccinic acid, ~nthr~nilic acid, 2-mercaptobenzothiazolylsuccinic acid [(~)Irgacor 252 (Ciba-Geigy)], 6-[4,6-bis(5-W O 97/01606 PCTnEPg6/02600 carboxypentylamino)-[1,3,5]-tria7in-2-ylamino]-h~nPc~rboxylic acid [~Reocor 190 (Ciba-Geigy)], furancarboxylic acid, pyrrolecarboxylic acid or py~.~7olPdi~rboxylic acid;
and ii) an amino~eilanP of the formula V, wherein the aminosilane of the formnl~ V is 3-aminoplopyll,iethoxysilane, 3-aminopropyll~i...Pthoxysilane, N-methyl-3-aminopLopy~ Pthoxysilane, 3-aminoplupyLllethyl(litothQxysilane~
3-aminopropyl~limethylethoxysilane~ N-allyl-3-aminopl~pyll~ ;...ethoxysilane, ~aminobutyltriethoxysilane, N,N'-dimethyl-3-aminoplopyllliethoxysilane, N,N'-dibutyl-3-aminopl~,~yll~;ethoxysilane, N,N'-(di-2-hydro~y~ yl)-3-aminoplopyl~itel~-oxysilane, bis[3-(triptho~ysilyl)propyl]a-m--ine~ 3-(2-aminoethylamino)p~l,yll. i.--ethoxysilane, 3-(2-~minoethylamino)p,opylll,ethyldimethoxysilane, 3-(6-aminohexylamino)plopyl~
methoxysil~ne, 3-[2-(2-~minoethylamino)ethylamino]~lol)yll~ Pthoxysilane~ amino-phellyll, illlpthoxysilane or 3-aminopropyleil~t~.~nP

Very special pl~ ce is given to coating compositions col.-l). isi~ as component (b) a salt and/or an amide derived from lauric acid with an ~minoeilanP. of the formula V, especi~lly 3-aminoprupyll.iPthoxysilane, 3-aminop,~lpyll.i...ethoxysilane, 3-amino-propyldietho~yhyd~o~ysilane, 3-aminopropyldihydroxyethoxysilane, 3-amino-pl~pyl~ y~o~ysilane, 3-aminopropyldimetho~yhydlo~ysilane, 3-aminopropyldihy~o~y-methoxysilane, 3-aminopropylcil~tranp~ 3-aminopl~pyl,llethykli~thoxysilane or 3-(2-~9minoethylamino)pl~pyll~ illlethoxysilane.

~mino.eilanP~e of the formula V in which Rlg and/or R20 are hydroxyl can readily undergo oligomerisation or polymeri.e~tion with e.lmination of water. The present invention therefore also provides coating compositions co--~ g as component (b) a salt and/or an amide derived from i) a polyacrylic acid, an acrylic acidlmaleic acid copolymer or a carboxylic acid of formula I and ii) an aminosilane of the formula V which, if at least one of the radicals Rlg and R20 is hydroxyl, can have an oligomeric or polymeric structure.

The salts and amides derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an aminosilane of the formula V
are suitable as corrosion inhibitors and adhesion promoters in coating compositions for protecting metallic s~lrfaces~ but also for pretreating metallic substrates. As such they can be added to all liquid or solid organic materials.

W O97/01606 PCT~EP96/02600 The sa ts are advantageously prepared in situ in the course of the preparation of the coating composition. There is therefore a7so interest in coating compositions in which c~mponent (a) is formed in situ during the prep~r~tion of the coating composition by separate addition of components (i) and (ii) and subsequent mixing of the coating composition.

The present invention also provides a process for the preparation of a coa~ng composition colnrri~ing a salt derived from i) a polyacry ic acid, an acrylic acid-maleic acid copolymer or a carboxy ic acid of the formula I and ii) an ~minosil~ne of the formula V, which cc,-,~, ;~s mixing an organic fi m-forming binder with at least one polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and at least one ~mino.~ nP. of the formula V.

The coating composition is preferably a surface-coating m~t~ l. It is especially~er~lably an aqueous surface-coating m~t.ori~7 Examples of surface-coating m~f~.ri~ are paints, inks or v~rni~hes. These alwayscomrri.ce an organic f~-forming binder in ~ddition to other, optional components.

Preferred organic film-forming binders are epoxy resins, polyul~lhalle resins, polyester resins, acrylic resins and copolymer resins thereof, polyvinyl resins, ph~nolic resins, aLlcyd resins or ~ ules of such resins.

Suitable organic film-forming binders of the coating composition are all cu.~tom~ry f~
formers for solvent-free or solvent-co~ ing~ but especially for aqueous, coatingcomposition.C Examples of such film formers are epoxy resins, polyurethane resins, amino resins or mixtures of such resins; a basic aqueous dispersion or a solution of an acidic resin.

Particular interest ~tt~chPs to organic film-forming binders for aqueous coatingcompositions, for eY~mI 1P. alkyd resins; acrylic resins; 2-component epoxy resins;
polyurethane resins; polyester resins, which are usually saturated; water-dilutable phenolic resins or derived dispersions; water-dilutable urea resins; resins based on vinyl-acrylic copolymers; hybrid systems based on epoxy acrylates, for çx~mrlç, More specifically, the aLkyd resins can be water-dilutable alkyd resin systems which can WO 97/01606 PCT~EP96/02600 be employed in air-drying form or in the form of stoving systems, optionally in combination with water-dilutable me.lAminP. resins; they may also be oxidatively drying, air-drying or stoving systems which ~'~qn be em~loyed optionally irl c--mbinAtion with aqueous dispersions based on acrylic resins or their copolymers, with vinyl AcetAtec, etc.

The acrylic resins can be pure acrylic resins, epoxy acrylate hybdd systerns, acrylic acid or acrylic ester copolymers, combinations with vinyl resins or copolymers of vinyl monom~rs such as vinyl acetate, stryrene or blltA~ one. These systems can be air-drying or stoving systems.

In combination wi~ appl~,pliate polyamine crocclinkin~ agents, water-AillltAble epo~cy ~ resins exhibit PYcellpnt mPchAni~Al and ~~h.q.mif~l reSict~n~e~ When liquid epoxy resins are used, the A~ldition of organic solvents to aqueous systems is unnPc~.scAry. The use of solid resins or solid-resin Ai.cpercions normAlly requires the a~iAition of small amounts of solvent in order to ih~ ve film form~tion.

Preferred epoxy resins are those based on aromatic polyols, especi~lly those based on bi.cph~onol.c. The epoxy resins _re employed in comhinAtion with crosclinking agents. The latter may in particular be amino- or hydlv~y-functional compounds, an acid, an acid anhydride or a Lewis acid. F.~Amrlçs thereof are polyamines, polyAminoAmiAec, polymers based on polys~llfitles, polyphP-nolc~ boron fluorides _nd their comrl~.x compounds, p.olyearboxylic acids, 1,2-dicarboxylic anhydrides, or pyromP.llitiC anhydride.

Polyurethane resins are derived from polyethers, polyesters and polyblltAfli~.nes with terminAl hydroxyl groups, on the one hand, and from AliphAtic or aromatic polyisocyanates on the other hand.

Examples of sllit~ble polyvinyl resins are polyvinylbutyral, polyvinyl acetate or copolymers thereof.

Suitable phenolic resins are synthetic resins in whose synthesis phenols are the principal component, i.e. in particular phenol-, cresol-, xylenol- and resorcinol-formAl(1ehyde resins, aLkylphenolic resins, and condensation products of phenols with acetaldehyde, furfurol, acrolein or other aldehydes. Modified phenolic resins are also of interest.

The coating compositions ean additionally comprise one or more components from the W O 97101606 PCT/~1,5.'~2600 group con~eieting of pi~mPnte, dyes, fillers, flow control agents, dispersants, thixotropic agents, adhesion promoters, antioxi~l~nt.c, light st~bili7Pnc and curing catalysts. They can also cnn~ain oth~Pr known anticorrosion agents, for e,Y~mplp~ anticorrosion pigmP.nt.e, such as phosph~tP- or borate-col~lA;-~;--g pigmP.nte or metal oxide pi~mpnts~ or other orgar~ic or inorganic corrosion inhibitors, for eY~mple salts of nitroisophth~lic acid, phosrhoric esters, intlllstri~l a-m-ines or substit~ted ben~c,l. ;~701~P~e.

The pi~mPnt.~ are, for eY~mrl~ dio,side, iron o~cide, ~ ;-~-.. bronze or phthalocyanine blue.

Fs~mplPs of fillers are talc, ~ min~ llminililm silicate, barytes, mica or silica. The corrosion inhihitors can also be applied to a carrier m~tPri~l M~t~ri~le suitable for this purpose are, in particular, pulverulent fillers or pigmpnts.

Flow control agents and thLxotropic agents are based, for eY~mrlp~ on mo~lifiP~ ~Pnl~ t s AtlhPcion promoters are based, for eY~mplP., on modifiPd silanes.

It is also advantageous to add basic fillers or pigmPnt.e, which in certain binder systems bring about a synergistic effect on the inhibition of corrosion. FY~mples of such basic fillers and piEmpnt~s are calcium carbonate or m~nP.,eillm carbonate, zinc oxide, zinc c&l~onate, zinc phosph~tP, m~gn~P~s~ oxide, ~lnmin~ in;~ phosph~tP. or mixtures thereof. Examples of basic organic pigmPnt.~ are those based on ~mino~nthr~quinone.

The corrosion inhibitors can be added to the surface-coating m~teri~l during itsproduction, for çY~mrlP. during the ~i~pprsion of the pigment by milling, or else the inhibitor is dissolved in a solvent and then stirred into the coating composition. The solutions of the corrosion inhibitors can also be used to pretreat the metal surface.

In the preparation of the organic film-forming binder by ~ tion polym~Pris~tion or polycon~len.~tion of m~nomer.c, the corrosion inhibitors can be mixed in with the monomers prior to polymerisation, either in solid form or in solution.

The salts and/or amides, or components (i) and (ii), are advantageously used in a quantity of from 0.01 to 20 % by weight, preferably frorn 0.05 to 5 % by weight and, in particular, from 0.1 to 5 % by weight, based on the overall solids content of the coating composition.

WO 97/01606 PcT/~ 6oo The surface-coating m~tPri~lc can be applied to the substrate by the custQm~ry methods, for çx~mple by spraying, dipping, brushing or by electrodeposition. Frequently, two or more coats are applied. The eorrosion inhibitors are prim~rily added to the b~cecQ~t ~primer), since they act in particular at the metal/coating intP~ e However, they ean also be added to the intermediate coat or topcoat as well. Depending on whether the binder is a physically, ehPmi~lly or oxidatively drying resin or a heat- or radiation-curing resin, the coating is eured at room tempelaLule or by heating (stoving) or by irr~ tion The surface-coating m~teri~l is preferably a primer for met~llic substrates, for e~qmr~lP
iron, steel, copper, zinc or ~11.l..;,~;l..,~, and their alloys.

In addidon to their anticorrosive action, the salts and/or amides derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~minocil~nP of the formula V have the advantage that they favourably influence the ~lhP~cion beLween coating and metal, exhibit no adverse effects on the storage stability of the novel coating compositionc, and are readily compatihle with the binder.

A p~ d embodiment of the present invention is therefore the use of the salts andamides derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~minoCil~np of the formula V as corrosion inhihitorc in coating compositions for met~llic Su~re~c~

The present invention also provides a method of protecting a corrodable metal substrate, whieh comp~.~ices applying to this substrate a coating composition compricing a) an organic film-forming binder and b) as corrosion inhibitor a) at least one salt and/or ,~) at least one amide derived from i) a polyacrylie acid, an acrylic acid-maleic acid copolymer or a carboxylie acid of the formula I and ii) a n aminosilane of the formula V, and tnen drying and/or curing the coating composition.

The invention likewise provides novel salts derived from i) a polyacrylic acid, an acrylic aeid-maleic acid copolymer or a carboxylic acid of the formula I

W O 97/01606 PCT/~l~5~ 6oo R1 Xl I T COOH (I) R3 Rs -- --m -- --n in which Rl is hydrogen, Cl-C2saLkyl, C2-C2saLkyl which is inte,l.l~led by oxygen or sulfur;
C2-C24alkenyl, C4-ClscycloaLkyl which is lln.c~lbstit~lt~d or substituted by Cl-C4aL~yl and/or cal~o-.yl; C5-Clscycloalkenyl which is un~ bs!~ rd or ~ub~ rd by Cl-C4alkyl and/or carboxyl; Cl3-C26polycycloalkyl, C~Cgphenylalkyl which is unsubstituted or .d on the phenyl ring by Cl-C4alkyl; -COR6, a 5- or 6-m~o-mbered heterocyclic ring which is unsubstituted or ~b~ d by Cl-C4alkyl, Cl-C4aL~oxy, halogen or carboxyl; a 5- or 6-membered heterocyclic ring which is benzo-fused and is ~ sli~
or ~ubslituled by Cl-C4aLkyl, Cl-C4~1ko~y, halogen or c~bo,~yl; or else Rl is a radical of the formula II, m or IV

R10~ (R12)~ S N~
R" R8 R14 ~) (m) (IV) R2, R3, R4 and Rs independently of one another are hydrogen, hydroxyl, Cl-Cl8aL~oxy, C2-Cl8aLkoxy which is interrupted by oxygen or sulfur; Cl-C25aLkyl, C2-C25aLkyl which is interrupted by oxygen or sulfur; C2-C24aL~enyl, C5-Clscycloalkyl which is unsubstituted or substituted by Cl-C4aLkyl; Cs-Cl5cycloaLkenyl which is unsllbstit~ d or substituted by Cl-C4aLkyl; phenyl or naphthyl which is ~ln.c~lbstituted or sllbstitllt~d by Cl-C4aLkyl;
C7-CgphenylaLkyl which is unsubstituted or substituted on the phenyl ring by Cl-C4aLkyl;
C10-Cl2naphthylaLLyl which is unsubstituted or substituted on the naphthyl ring system by Cl-C4aLkyl; or are -COR6, with the proviso that, if one of the radicals R2, R3, R4 and Rs is hydroxyl, the other radical attached to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and Rs, together with the carbon atom to which they are attached, form an unsubstituted or Cl-C4alkyl-substituted Cs-Cl2cycloaLkylidene ring, CA 0222l776 l997-ll-2l WO 97/01606 PCT~EP96/02600 R6 is hydroxyl, Cl-Cl8aLkoxy, C2-Cl8aLoxy which is interrupted by oxygen or sulfur; or is --N or--N o 'R16 \--R7, R8, Rg, Rlo and Rll independently of one another are hydrogen, hydlu~yl, halogen, nitro, cyano, CF3, -COR6, C~-C25aLcyl, C2-C25aLyl which is i,~ upLed by oxygen or sulfur; C1-C2sh~lo~lkyl~ Cl-CI8alkoxy, C2-CI8alkoxy which is inL~llul~led by oxygen or sulfur; Cl-Cl8aLcylthio, C2-C24alkenyl, C5-Clscycloalkyl which is ~ ub~ ed or substitntPd by Cl-C4aLcyl; C5-Clscycloalkenyl which is unsubstituted or substituted by Cl-C4aL~yl; phenyl or naphthyl which is Im~llhstitutP.d or substitllted by Cl-C4alkyl;
CTCgphenylaLyl which is un.cubstihltPd or substitut~Pd on the phenyl ring by Cl-C4alkyl;
C1O-Cl2naphthylaLyl which is nn.~l1bstit~ltPd or s~lbstit~ltPd on the llapllLllyl ring system by Cl-C4aLcyl; pheno~ty or naphthoxy which is lln.~.lb~ d or ~..,bsl;I..~d by Cl-C4aLLyl;
C7-CgphenylaLoxy which is l-n.~i~.b5l i I uled or substitutP.d on the phenyl ling by Cl-C4aLcyl; C10-Cl2naphthylaLcoxy which is un.~lbstit~tP~ or s~ Pci on the naphthyl ring system by Cl-C4aLlcyl; or else the radicals R8 and R9 or the radicals Rg and Rlo or tne radicals Rlo and Rll or tne r~dic~ls R7 and Rll, togetner the carbon atoms to which they are ~tt~hP,r~, form an ~ln.~ubstitlltPd or Cl-C4aLkyl-, halogen- or Cl-c4aLcoxy-~ubs~luLed benzo ring, with the proviso that at least one of the r?~iç~l~ R7, R8, Rg, Rlo and Rll is hydrogen, Rl2 is hydlo~yl, halogen, nitro, cyano, CF3, Cl-C25aLkyl, C2-C25aLkyl which is inLellul)led by oxygen or sulfur, Cl-C2sh~lo~lkyl, Cl-CI8aL~oxy, C2-CI8aLkoxy which is inLellu~,led by oxgyen or sulfur; Cl-CI8aLylthio or C2-C24aLenyl, Rl3 and Rl4 indepe.n-lently of one another are hydrogen, Cl-C2saLyl, Cl-CI8aLkoxy or -Y-(CH2),jCOR6, Rls and Rl6 independently of one another are hydrogen, Cl-C2saLcyl, C3-C2saLcyl which is ui)ted by oxygen or sulfur; C2-C24aLenyl, C5-CI5cycloaLkyl which is unsubstituted or substihltPd by Cl-C4aLkyl; phenyl or naphthyl which is lln.~ubstihltPd or sllbstitutPd by Cl-C4alkyl, X1 is a direct bond, oxygen, sulfur, / =~, Cl-Cl8alkylene, C2-C18aLkylene which is interrupted by oxygen or sulfur; C2-CI8aLenylene, C2-Cl8aLynylene, C2-C20aLkylidene, C7-C20phenylaLkylidene or Cs-C8cycloaLkylene, with the proviso that, if m and n are 0, X
is other than oxygen and sulfur, Y is oxygen or ~Ra, Ra is hydrogen or Cl-C8aLkyl, _ m and n indepen(lP.ntly of one another are integers from 0 to 10, p is an integer from 0 to 4, s is an integer from 1 to 8, and ii) an ~mino~ np of the formlllA V

R~7 ~(R-9)b N--X2 S~ (V) R-8 (R2o)4 a b --a in which R17 and Rl8 indepPntlP.ntly of one another are hydrogen, Cl-C2saLkyl, 2-hydiu~yc;~lyl, C3-C25aLkyl which is intellu~ d by oxygen or sulfur; C2-C24alkenyl or ~ (R~Y)b (R20)4 - b Rlg is Cl-C2salkyl, C2-C25alkyl which is ill~llup~d by oxygen or sulfur; hydroxyl, Cl-Cl8alkoxy orC2-C24aL~enyl, R20 is hydroxyl, Cl-Cl8alkoxy or C2-Cl8aL~coxy which is illl#llu~L~d by oxygen or sulfur, and, if a and b togpth~r are 1, three rA~ R20 together are N(CH2CH20-)3, R2l is hydrogen or Cl-C8aL~cyl, X2 is Cl-Cl8aLkylene, C2-C20aL~cylidene, C7-C20phenylaLkylidene, Cs-C8cycloaL~ylene, phenylene or naphthylene which is ...-x..ks~il,.l~d or ~IL.~ led by Cl-C4aLkyl; or is C4-Cl8aLkylene which is inlell.~d by oxygen, sulfur or ~R21, with the proviso that never two nitrogen atoms are attached to the same carbon atom, ais 1 or2,and bisO, 1 or2.

Preferred groups of novel salts derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and an ~minosil~nP of the formula V
correspond to the preferences expressed above for the coating compo.citi~-n.c.

Prefe}ence is ~d~lition~lly given to salts derived from i) a carboxylic acid of the formula I
in which CA 0222l776 l997-ll-2l W O 97/01606 PCT~EP96/02600 -26-Rl is hydrogen, Cl-C2saL~yl, C2-C25aLkyl interrupted by oxygen or sulfur; C2-C24aLkenyl, C4-ClscycloaL~cyl which is unsubstitllted or ~ub~LiLuL~d by Cl-C4alkyl; Cs-CIscycloaLkenyl whi~ is un~lb~tit~lt~d or ~ i luled by C1-C4alkyl; Cl3-C26polycycloalkyl, C~CgphenylaLkyl which is un.~ubstihlted or sllbstituted on the phenyl ring by Cl-C4allyl;
-COR6, a 5- or 6-membered heterocyclic ring which is lln~ubstihlted or sul.~ ed by Cl-C4alkyl, Cl-C4aLkoxy, halogen or carboxyl; a 5- or 6-membered heterocyclic ring which is benzo-fused and is unsubstituted or ~llr~ ed by Cl-C4alkyl, Cl-C4aLkoxy, halogen or carboxyl; or else Rl is a radical of the formula II, m or IV

R~o~ tR12)~C ~>-- N~= N~_ tII) tm) (IV) R2, R3, R4 and Rs inde~en(:lently of one another are hydrogen, llyd~ yl, Cl-Cl8alkoxy, CrCl8aLI~oxy which is illlellupt~d by oxygen or sulfur; Cl-C2salkyl, C2-C2salkyl which is illL~llu~Led by oxygen or sulfur; C2-C24alkenyl, (:~5-Clscycloalkyl which is nn~ubstitllted or substituted by C1-C4aLkyl; Cs-ClscycloaLlcenyl which is nn.~ubstitllted or sllhstitllted by Cl-C4alkyl; phenyl or naphthyl which is unsubstituted or substitllt~o.d by Cl-C4alkyl;
CTCgphenylaLkyl which is uns~lbstituted or substinlted on the phenyl ring by C1-C4aLkyl;
C10-Cl2naphthylaLkyl which is unsubstituted or ~ub~LiLuL~d on the naphthyl ring system by C1-C4aLI~yl; or are -COR6, with the proviso that, if one of the radicals R2, R3, R4 and Rs is hydlohyL the other radical attached to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and Rs, together with the carbon atom to which they are ~tt~h~d, form an unsubstituted or C1-C4aLkyl-substituted Cs-C12cycloaLkylidene ring, R6 is hyd~ yl, C1-C18aL~coxy, C2-C18aLkoxy which is inte~l u~ d by oxygen or sulfur; or ~ 16 R7, R8, Rg, Rlo and R1 1 independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, Cl-C2saLkyl, C2-C25alkyl which is intellupled by oxygen or sulfur; C1-C2~h~lo~lkyl, C1-CI8aLLoxy, C2-Cl8aL~coxy which is interrupted by oxygen or sulfur; Cl-Cl8aL~cylthio, C2-C24aLkenyl, Cs-Cl5cycloaLkyl which is unsubstituted or sub~Liluled by Cl-C4all~yl; Cs-C15cycloalkenyl which is unsubstituted or substituted by wo 97/01606 PCTIEW6/02600 Cl-C4aLkyl; phenyl or naphthyl which is unsubstituted or substituted by Cl-C4aLkyl;
C7-Cgphenylalkyl which is unsnbstit~lted or substituted on the phenyl ring by Cl-C4aL~cyl;
C~c-Cl2naphthylaLkyl which is unsubstituted or substituted on the naphthyl ring system by Cl-C4aLkyl; phenoxy or naphthoxy which is unsubstituted or ~I,s~ cl by Cl-C4alkyl;
C7-Cgphenylalkoxy which is ~lnsll~stihlt~d or substitllt~.d on the phenyl ring by Cl-C4aLkyl; C1O-Cl2naphthylalkoxy which is lm.~lbstitntPd or ~;u~ -led on the naphthyl ring system by Cl-C4aLkyl; or else the radicals R8 and Rg or the r~lic~ls Rg and Rlo or the r~lical.~ Rlo and Rll or the radicals R7 and Rll, together the carbon atoms to which they are attached, form an un~bsfitllt~.d or Cl-C4aLkyl-, halogen- or Cl-C4alkoxy-substituted benzo ring, with the proviso that at least one of the radicals R7, R8, Rg, Rlo and Rll is hydrogen, Rl2 is hydroxyl, halogen, nitro, cyano, CF3, Cl-C2saLkyl, C2-C2saL~yl which is ih~ u~L~d by oxygen or sulfur; Cl-C2sh~lo~lkyl~ Cl-Cl8aL~coxy, C2-Cl8aL~oxy which is inlellul)~ed by oxgyen or sulfur; Cl-Cl8aL~ylthio or C2-C24aLkenyl, Rl3 and Rl4 independently of one another are hydrogen, Cl-C2saLkyl, Cl-Cl8alkoxy or -O-(CH2)~cOR6~
RlS and Rl6 independently of one another are hydrogen, C~-C2saLl~yl, C3-C25alkyl which is llu~l~d by oxygen or sulfur; C2-C24aL~enyl, Cs-ClscycloaLkyl which is un~ub~lu~dor sub~ uled by Cl-C4aLkyl; phenyl or naphthyl which is uns~l~stitut~.cl or ~ul)~lilul~d by Cl-C4aLkyl, Xl is a direct. bond, oxygen, sulfur, ~C =O, Cl-Cl8aLkylene, C2-Cl8aL~cylene which is illlellul)led by oxygen or sulfur; C2-Cl8aLkenylene, C2-Cl8alkynylene, C2-C20aLkylidene, C~C20phenylalkylidene or C5-C8cycloaLlcylene, with the proviso that, if m and n are 0, X
is other than oxygen and sulfur, m and n in(lP.pendently of one another are integers from 0 to 10, p is an integer from 0 to 4, s is an integer from 1 to 8, and ii) an aminosilane of the formula V in which Rl7 and Rl8 independently of one another are hydrogen, Cl-C2saL~yl, 2-hydroxyethyl, C3-C25aLkyl which is illLe,lupted by oxygen or sulfur; or is C2-C24aLI~enyl or ~, (R~g)b --X2- Sl (R20)4 - b Rlg is C~-C25alkyl, CrC25alkyl which is interrupted by oxygen or sulfur; or CA 0222l776 l997-ll-2l WO 97/0l606 PCT/EP96/02600 C2-C24aLkenyl, R20 is hydroxyl, Cl-Cl8alkoxy or C2-Cl8aLkoxy which is h~ lul~ted by oxygen or sulfur;
R2l is hydrogen or Cl-C8aLkyl, X2 is Cl-Cl8aL~cylene, C2-C20alkylidene, C7-C20phenylaLkylidene, Cs-C8cycloaL~cylene, phenylene or naph~lylene which is un.cllbstit~ltçd or substit~ltPd by Cl-C4alkyl; or is C4-Cl8aLkylene which is inL~llu~l~d by oxygen, sulfur or ~N--R21, with the proviso that never two nitrogen atoms are attached to the same carbon atom, ais l or2,and bisO, lor2.

Also of interest are salts derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii~ an ~mino.~ ne of the formula V in which Rl is Cl-C2saL~yl, C2-Cl6aL~enyl, 2-carboxy 1-methylcyclohexenyl, cyclohexyl, benzyl, -COR6 or a radical of the formula II or m R,l R, (~) R1o~ (Rl2)~ (~
Rg 8 R2, R3, R4 and Rs independently of one another are hydrogen, Cl-C8aL~cyl, phenyl, benzyl or -COR6, ,R,5 R6 is hydroxyl, Cl-C4aLkoxy or --N~R

R7 is hydrogen or Cl-C4aL~cyl, R8 is hydrogen, hydroxyl, Cl-C4aLIcyl, nitro or chlorine, Rg is hydrogen or Cl-C4aLkyl, Rlo is hydrogen, Cl-C4aLkyl, nitro, chlorine or -COR6, Rll is hydrogen or Cl-C4aLkyl, Rl2 is chlorine, Cl-C4alkyl or Cl-C4aLl~oxy, Rls and Rl6 independently of one another are hydrogen or Cl-C4alkyl, Rl7 and Rl8 indepçndently of one another are hydrogen or Cl-C4alkyl, Rlg is Cl-C6alkyl, C2-C6aLkenyl, hydroxyl or Cl-C4aL~oxy, R20 is ~lydioxyl or Cl-C4aLkoxy, and, if a and b together are l, three radicals R20 together -W O 97/01606 PCT~EP96/02600 are N(CH2cH20-)3~
R2l is hydrogen or C1-C4aLkyl, Xl is a direct bond, sulfur, ~C = O or Cl-ClOaL~cylene, with the proviso that, if m and n ~ are O, Xl is other than sulfur, X2 is C2-C6aLIcylene, cyclohexylene, or C4-C8aLI~ylene which is ih~ uyl~d by ~R2l, with the proviso that never two nitrogen atoms are attached to the same carbon atom, a lSl, bisOor 1, m and n indepçn-lçntly of one another are O, 1 or 2, and p is O or 1.

There is particular interest in salts derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~minocil~ne of the formula V in which Rl is Cl-Cl8alkyl, 2-c~l.o~y-4-methylcyclohexenyl, -COR6 or a radical of the formula II
orm ~) R10~ (R12~c S
R~ R8 R2 is hydrogen, R3 is hydrogen or -COR6, R4 and Rs are hydrogen, R6 is hydroxyl, R7 is hydrogen, R8 is hydrogen, hydroxyl, Cl-C4alkyl, nitro or chlorine, Rg is hydrogen, Rlo is hydrogen, Cl-C4aLkyl or nitro, Rll is hydrogen, Rl7 and Rlg are hydrogen or methyl, Rlg is Cl-C4alkyl, hydroxyl or Cl-C4aLkoxy, R20 is hydroxyl or Cl-C4aL'coxy, and, if a and b together are 1, three radicals R20 together Wo 97/01606 PCT/EP96/02600 are N(CH2cH2O-)3 R2l is hydrogen, Xl is a direct bond, sulfur, ~C = O or Cl-C8alkylene with the proviso that, if m and n are 0, Xl is other than sulfur, X2 is C2-C4alkylene, or C4-C6alkylene which is illle,l~ted by ~R2" with the proviso that never two nitrogen atoms are att~ch~d to the same carbon atom, ais 1, b is 0 or 1, m and n independently of one another are 0 or 1, and pisO.

The novel salts and amides derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I and ii) an ~minosil~ne of the forrnnl~ V
can be prepared in a manner known per se.

Equimolar q~ il;cs of the c~Lu~ylic acids of the formula I and amino~ n~s of ~e formula V are preferably mixed with one another in a le~pe~ range from 10 to 80~C, in particular at from room temperature to 6Q~C. Where the carboxylic acid of the formula I
has two or more -COOH groups in the molecule, one equivalent of ~mino.cil~nP. isemployed for each individual -COOH group. Where the rç~ct~ntS are partially crys~llin~, the formation of salt or of amide is advantageously carried out in a solvenL Suitable solvents are water, organic solvents or aqueous-organic solvents. Examples of organic solvents are ketones, for example acetone, methyl ethyl ketone or cyclohP-~nonP; esters, for example ethyl acetate or isopropyl acetate; alcohols, for çx~mple methanol, ethanol, isopro~allol, n-butanol, glycol, glycerol, ethylene glycol or methoxyethanol;
hydrocarbons, for example pentane, hexane, heptane, octane, benzene, toluene or xylene;
ethers, for example diethyl ether, dibutyl ether, tetrahydrofuran or (1io~r~nç or amides, for example dimethylfonn~mi~le, dimethylacetamide or N-methylpyrrolidone.

The carboxylic acids of the formula I are known in the literature and their preparation is described in the references mentioned at the outset. Numerous carboxylic acids of the formula I are commercially available.

Polyacrylic acids or acrylic acid-maleic acid copolymers are known in the literature and are described for exarnple in "Ullmann's Encyclopedia af Industrial Chemistry, Volume A

CA 0222l776 l997-ll-2l W O 97/01606 PCT/EPg6/02600 21", pages 143-156 (1992).

The aminosil~nP~ of the formula V are l~ewise known in the literature or can be prepared in analogy to J.L. Speier et al., J. Org. Chem. 36, (21), 3120-3126 (1971); L. Birkofer et al., Chapter 10, pages 655 to 751 in S. Patai, Z. Pappoport "The ChPmi~try of Organic Sili-con Compounds", John Wiley & Sons Ltd., 1989; or E.P. PhlPd<lem~nn, "Silane Coupling Agents", Plenum Press 1982, pages 1-233. Many of the specifically pl~r~ d ~minosil~nPs are obtainable from Fluka AG.

The eY~mples which follow illllstr~tP the invention m more detail. Parts and pe,~;el~la~es are by weigh~

Example 1: General instructions for the preparation of the salts deAved from thecarboxylic acid of the forrnula I and from the ~mino-cil~ne of the formula V [Compounds (101) to (117), Table 1].

0.20 mol of aminosilane of the formula V is charged under a nitrogen ~tmosphPre to a sulfonating flask fitted with n~PCh~niC?l stirrer and thermometer. 0.20 mol of the relevant carboxylic acid of the formula I is then added with thorough stirring, and stiIring is continl-ed at room temperature for one hour. In the case of sebacic acid [Compound (112)]
and of 2-mercaptobenzothiazolylsuccinic acid [~)Irgacor 252 (Ciba-Geigy), [Compound (113)] 2 equivalents of aminosilane are used. If the c;alb~,~ylic acid of the formula I has not dissolved completely, the r~tion mixture is heated briefly at from 40 to 60~C. The novel salts are obtained in ql-~ntit~tive yield. The results are collated in Table 1.

CA 0222l776 l997-ll-2l W O 97/01606 -32- PCT~EP96/02600 Table 1:
CompoundCarboxylic ~mino~ np A C (%), H ~%), N (%) formula I formula V the salt (calculated/found) 101 Acetic acid A colourless liquid 46 97 9 61 4 99 102 acid A ye~owish liquid 54 66 1061 3 98 103 Lauric acid A colourless oil 59 81 11.23 3 32 104 Stearicacid A colourless oil 64o3 1166 277 105 Benzoic acid A colourless oil 55 97 8 56 4 17 106 S~icylic acid A colourless oil 53 08 8 44 3 81 107 acid A white powder 55 82 8 69 3 75 108 o-Nitro- A ye~ow oil 49.47 7.26 7.21 benzoic acid 48.62 7.30 7.11 109 p-Nitro- A yellow powder 49.47 7.26 7.21 benzoic acid 48.81 7.38 7.18 110 o-Ch1oro. A yellow Tesin 50.85 7.40 3.70 benzoic acld 50.38 7.60 3.59 111 D A yellowish liquid 58 16 8 53 3 32 112 Sebacic acid A* white powder 5070 9 90 4 10 113 E A* orange oil 47 6i 7 74 5 66 114 D B yellowish liquid 59 01 8 60 3 65 115 Benzoic acid B yellow oil 57 44 8 67 4 47 116 D C yellow oil 54 50 8 19 6 87 CA 0222l776 l997-ll-2l W O 97/01606 PCT~E~S-'~U~C

Table 1: (continll~tion) Carboxylic~mino.~ n~ Appearance of C (%), H (~o), N(%) Compound acid of the of the the salt (c~lcul~t~d/found) formula Iformula V
117 E C* orange resin 44 05 7 26 9 73 * 2 equivalents of ~mino.eil~ne of the formula V employed A = 3-Ammopropyltr~ethoxysilane (Fluka 09324) B = 3-Aminopropylmethyldiethoxysilane (E luka 09309) C = 3-(2-~minoefhylamino)~l~yl~ ethoxysilane (E;luka 06668) D = 3-(4-Methylbenzoyl)propionic acid E = 2-Mercaptoben7.0thi~7Qlylsuccinic acid [~)Irgacor 252 (Ciba-Geigy)]

F~mr)le 2: Preparation of the salt derived from lauric acid and 3-aminopropyldihydroxy-ethoxysilane ~Compound (118)].

0.10 mol of 3-aminopropyltriethoxysilane is charged under a nitrogen atmosphere to a s llfc-n~tin~ flask. 0.20 mol of water and 0.10 mol of lauric acid are then added with thorough stirring, and stirring is continlled at room temperature for one hour. The salt derived from lauric acid and 3-aminopropyldihydroxyethoxysilane [Compound (118)] is obtained in qll~ntit~tive yield as an 80 % solution in ethanol.

Example 3: Preparation of the salt derived from lauric acid and 3-aminopropylt.ihydroxy-silane [Compound (119)].

0.10 mol of 3-aminopropyltriethoxysilane is charged under a nitrogen atmosphere to a sulfonating flask. 0.30 mol of water and 0.10 mol of lauric acid are then added with thorough stirring, and stirIing is continued at room temperature for one hour. The salt derived from lauric acid and 3-a~inopropyltrihydroxysilane [Compound (119)] is obtained in quantitative yield as a 72 % solution in ethanol.
r Example 4: Preparation of the amide derived from lauric acid and 3-aminoplo~yl ethoxysilane [Compound (120)].

0.10 mol of lauroyl chloride is added dropwise with thorough stirring at 0~C to a solution CA 0222l776 l997-ll-2l W O 97/01606 PC~ 7~C

of 0.10 mol of 3-aminopropyltriethoxysilane and 0.10 mol of triethylamine in S00 ml of tolllenP. The sn~pencion is then stirred at room temperature for two hours. The triethylamine hydro~hk)ri~lP is filt~ed off and the filtrate is con~nt-~t~d on a rotary evaporator under vacuum. The amide derived from lauric acid and 3-aminop~ yllliethoxysilane [Compound (120), white wax, yield 86 %] is obtained.Elemental analysis: calculated for C2lH4sO4SiN: C 62.48; H 11.24; N 3.47 %. found:
C 62.55; H 11.17; N 3.20 %

CH3(CH2)l0CONHCH2CH2CH2Si(OCH2CH3)3 (120) F~x~mrle 5: Prep~r~til~n of a 1:1 salt~amide mixture derived from lauric acid and 3-amino-propyltriethoxysilane [Compound (121)].

0.10 mol of 3-aminopropyltriethoxysilane and 17.2 g of ethanol are charged under a r~itrogen atmosphere to a sulfonating flask. O.OS mol of lauric anhydride is then added with thorough stirring, and stirring is conl;.~.~ed at room ~ "c for one hour. A 1:1 saltlamide mixture derived from lauric acid and 3-amino~ro~ iethoxysilane tCompound (121)] is obtained as a 70 % solution in ethanol ~50 parts of compound (103) and S0 parts of compound (120)].

Fy~mr)lP 6: Prep~r~stion of a mixed amide salt derived from succinic acid and 3-amino-propyltriethoxysilane [Compound (122)].

0.10 mol of 3-amin~plupylLiiethoxysilane is charged under a nitrogen atmosphere to a sulfonating flask. O.OS mol of succinic anhydride is then added with thorough stirrin,~, and stirring is contin~d at room temperature for one hour. The desired amide salt CCompound (122)] is obtained in q~l~n~it~tive yield as a colourless liquid. F,lemçnt~l analysis:
calculated for C22HsoO9Si2N2: C 48.68; H 9.28; N 5.16 %. found: C 46.92; H 9.17; N

5.20 %.

(CH3CH20)3SiCH2CH2CH2NHCOCH2CH2COO- H3N+CH2CH2CH2Si(OCH2CH3)3 (122) Exam~le 7: Preparation of a mixed amide salt derived from phthalic acid and 3-arnino-propyltriethoxysilane [Compound (123)].

Wo 97/01606 PCT/EP96/02600 0.10 mol of 3-aminop,opylL-iethoxysilane is charged under a nitrogen atmosphere to a suLfo~tin~ fl~ O.OS mol of phthalic anhydride is then added with thorough stirring, and stirring is continued at room temperature for one hour. The desired amide salt [Compound (123)] is obtained in q-J~ tiv~ yield as a colourless liquid. F.1PmP.nt~1 analysis: calcu-lated for C26H50OgSi2N2 C 52.85; H 8.53; N 4.74 ~. found: C S1.48; H 8.27; N 4.76 %.

~ ~NHCH2CH2CH2Si(OCH2CH3)3 (123) COO H3NCH2CH2CH2Si(OCH2CH3)3 F~mrle 8: Preparation of a mixed amide salt derived from 4-methyl~cyclohPYenP-1,2-dicarboxylic acid and 3-aminopropyltriethoxysilane [Compound (124)].

0.10 mol of 3-aminol~lopyllliethoxysilane and 6.0 g of ethanol are charged under a r~itrogen atmosphere to a ulfon~ting flask. O.OS mol of 4-methyl-4-cyclohPlrPnP-1,2-dicarboxylic anhydride is then added with thorough stirring, and stilTing is continue~l at room tempe~ for one hour. The desired amide salt [Compound (124)] is obtained in ~u~ntit~tive yield as an 80 % solution in ethanol.

,,~ --NHCH2CH2CH2Si(OCH2CH3)3 (124) H3C Coo H3NCH2CH2CH2Si(OCH2CH3)3 Example 9: Preparation of a mixed amide salt derived from 2-dodecenylsuccinic acid and 3-aminopropyltriethoxysilane [Compound (125)].

0.10 mol of 3-aminopropyltriethoxysilane and 11.2 g of ethanol are charged under a nitrogen atmosphere to a sulfonating flask. 0.0~ mol of 2-dodecenylsuccinic anhydride is then added with thorough stirring, and stirring is continued at room temperature for one 6 PCT~EP96/02600 hour. The desired amide salt [Compound (125)] is obtained in q--~ntit~ive yield as a 70 %
solution in ethanol.

2-Dodecenyl C
~ --NHCH2CH2CH2Si(OCH2CH3)3 (125) ~ COO H3NCH2CH2CH2Si(OCH2CH3)3 Flr~~~nple 10: Preparation of a 1: 1 amide/salt mixture derived from lauric acid, 3-amino-propylL~iethoxysilane and 3-ami loplvpyldietho~yllydroky~ilane [Compound (126)].
A 70% soluton of compound (103) [Example 1] in ethanol is boiled under reflux for 4 hours under a nitrogen atmosphere. An appr~ ately 1: 1 ~ e [Compound (126)] ofthe compound (120) [Example 4] and of the Compound (127) is obtained as an a~ .lo~i.,.~tP.ly 70% solution in ethanol.

,, IocH2cH3 CH3(CH2)10COO H3NCH2CH2CH2 Si OH (127) Example 11: Preparation of a 7:3 amide/salt mixture derived from lauric acid, 3-amino-plopylL,iethoxysilane and 3-aminopropyldiethoxyhy~o~Lysilane [Compound (128)].

A 70% solution of compound (103) [Fx~mple 1] in ethanol is boiled under reflux for 8 hours under a nitrogen atmosphere. An appl~Ailllately 7:3 mixture [Compound (128)] of the compound (120) ~Example 4] and of tne Compound (127) is obtained as an approAilllately 70% solution in ethanol.

Example 12: Prepa;ation of the salt derived from lauric acid and 3-aminopropylsilatrane [Compound (129)].

0.10 mol of 3-aminopropylsilatrane [US-A-4 048 206, Example 243 and 18.6 g of ethanol are charged under a nitrogen atrnosphere to a sulfonating flask. 0.10 mol of lauric acid is then added witn thorough stirring, and stirring is continued at room temperature for one W O 97/01606 PcT/~5l~6oo hour. The salt derived from lauric acid and 3-aminopropyl~ tr~ne [Compound (129)] is obtained in ~ tive yield as a 70% solution in ethanol.

F~mple 13: Prep~r~tiorl of the .~ tr~n~mi~le salt derived from lauric acid and 3-aminopropyl~ tr~nP [Compound (130)].

0.10 mol of 3-aminopropyltriethoxysilane~ 0.10 mol of triethanol~minP. and 0.50 ml of a 3% sodium methylate solution are charged under a nitrogen ~tmo~q~hP.re to a sulfonating flask and are heated to 60~C. The homogeneous reaction solution is stirred at 60~C for 2 hours and then cooled to room temperature. Subsequently, 0.10 mol of lauric anhydride is added with thorough stirring, and stirring is then c- ntinued at room temp~ u.e for one hour. The sil~ n~.ide salt [Compound (130)] is obtained as an 82% solution in ethanol.

o CH3(CH2)10CONHCH2CH2CH2 S;--O~\~NH OOC(CH2)-0CH3 (130) O

Example 14: Preparation of the salt derived from lauric acid and N,N'-dimethyl-3-aminopropyltrimPth-)xysilane [Compound (131)].

In analogy to Example 1, the salt [Compound (131)] is prepared from 0.10 mol of lauric acid and 0.10 mol of N,N'-dimethyl-3-aminol,lopylll ill,ethoxysilane. F.1PmPnt~1 analysis:
calculated forC20H4sOsSiN: C 58.93; H 11.13; N 3.44 ~. found: C 58.94; H 11.07;
N 3.22 %.

Example 15: Preparation of the salt derived from polyacrylic acid (MW about 2000) and 3-aminopropyltriethoxysilane tCompound (132)].

9.8 g of polyacrylic acid (Aldrich; molecular weight about 2000; 10.2 mol of COOEVkg) and 33 g of ethanol are charged under a nitrogen atmosphere to a sulfonating flask.
1.0 mol of 3-aminopropyltIiethoxysilane is added with thorough stin ing, and stiiTing is then continued at 40~C for 2 hours. The salt derived from the polyacrylic acid and 3-aminopropyltriethoxysilane [Compound (132)] is obtained as a 50% solution in ethanol.

CA 02221776 1997-ll-21 W O 97/01606 PCTi~l,.~.~26C-Example 16: Preparation of the salt derived from polyacrylic acid (MW about 20 000) and 3-aminopropyltriethoxysilane [Compound (133)].

7.1 g of polyacrylic acid (Aldrich; molecular weight about 20 000; 13.3 mol of COOH/kg) and 30.8 g of ethanol are charged under a nitrogen ~tmosphPre to a slllfon~in~ flask.
0.10 mol of 3-amino~ pyllliethoxysilane is added with thorough stirrin,~, and stirring is then continlled at 40~C for 2 hours. The salt derived from the polyacrylic acid and 3-aminopropyltriethoxysilane [Compound (133)] is obtained as a 50% solution in eth~no P,~mple 17: Preparation of the salt derived from polyacrylic acid (MW about 250 000) and 3-amino~ ylL-iethoxysilane tCompound (134)].

7.3 g of polyacrylic acid (Aldrich; molecular weight about 250 000; 13.7 mol of COOH/kg) and 91.5 g of ethanol are char~ed under a nitrogen ~tmoSph~re to a sulfonating flask. 0.10 mol of 3-amino~lu~yllliethoxysilane is added with thorough stinin~, and stirring is then c~ ed at 40~C for 2 hours. The salt derived from the polyacrylic acid and 3-amin~,plo~ oxysilane [Compound (134)] is obtained as a 25% solution in eth~nol.

Example 18: Preparation of the salt derived from acrylic acid-maleic acid copolymer (MW
about 3000) and 3-aminopropyltliethoxysilane [Compound (135)].

7.5 g of acrylic acid-maleic acid copolymer (Aldrich; molecular weight about 3000;
13.3 mol of COOH/kg) and 71 g of ethanol are charged under a nitrogen atmosphere to a snlfQn~tin~ flask. 0.10 mol of 3-aminopropyltriethoxysilane is added with thorough stirring, and stirring is then continued at 40~C for 2 hours. The salt derived from the acrylic acid-maleic acid copolymer and 3-aminopropyltriethoxysilane [Compound (135)]
is obtained as a 30% solution in ethanol.

Example 19: Testing of the novel salts in a water-dilutable 2-component epoxy resin anticorrosion primer based on Beckopox EP 384 W/Beckopox EP 075/Beckopox EH 623 W as corrosion inhibitors.

The coating composition based on Beckopox EP 384 W/Beckopox ~P 075/Beckopox EH 623 W is prepared by employing components 1 to 8 (form~ tion without corrosion inhibitor) or components 1 to 9 (folmulation with corrosion inhibitor) in the stated W O 97/01606 PCT~EP96/02600 -39-sequence (component A, cf. Table 2). The ~u~l~y in which the novel corrosion inhibitors are employed is based on the overall solids content of the total formulation without corrosion inhihitt)r (overaU solids content: 62%). Accordingly~ for e~r~mrlP, an addition of O.S~o corrosion inhibjtor to 166.7 g of primer implies a quantity of 0.51 g.

Table 2: Water-dilutable 2-component epoxy resin anticorrosion primer based on Beckopox EP 384 W / Beckopox EP 075 / Beckopox EH 623 W
Composition % by weight Co . u.-ent A:
1) Beckopox EH 623 W(80 % supply forrn)a) 14.4 2) Deionised water 29.2 3) TaLIcum AT Extrab) 13.~
4) B~yÇ~llo~ 130 MC) 12.0 S) Millicarbd) 27.3 6) Bentone SD2e) 0-70 7) Borchigel L 75 (25 % supply form)f)1.70 8) Additol XL 270g) 0 9 9) Novel corrosion inhibitor Total 100.00 Component B:

10) Beckopox EP 384 W(54 % supply form)h) 63.0 11) Beckopox EP 075i) 3.7 a) ~)Beckopox EH 623 W: polyamine hardener (Hoechst AG); b) (~)TaLkum AT Extra:
Norwegian; c) @)Bayferrox 130 M: iron oxide red ~Bayer AG); d) ~Millicarb: calcium carbonate (Omya); e) (~)Bentone SD 2: anti-settling agent (Kronos Titan GmbH); f) (~3)Borchigel L 75: thickener/rheology improver (Gebr. Borchers AG); g) ~)Additol XL
270: anti~oating/dispersion auxiliary (Hoechst AG); h) ~Beckopox EP 384 W: epoxy W O 97/01606 PCT~EP96/02600 resin (Hoechst AG); i) (g)Beckopox EP 075: reactive diluent (polypropylene glycoldiglycidyl ether, Hoechst AG).

The resulting cull~pollenl A (formnl~tion with and without corrosion inhibitor) is dispersed to a particle finP.n~..cs < 15 I m using a horizontal ball mill. The result of ~licpçr.cior~ is assessed by clPte~ ....lli--g the grindometer value (ISO 1524).

For application, 100 g (formnl~tion without anticorrosion additive) or 100 + X g(formulation with corrosion inhibitor) are mixed with 66.7 g of component B. To adjust to the desired spray viscosity, the coating m~tPri~l is diluted with ~Pminpralized water. It is applied to steel panels (19 x 10.5 cm) of the Bonder type (cold-rolled degreased steel;
m~nnf~ch-rer: Chemetall, Frankfurt am MainlGermany) in a coat thicl~nPss which, after drying, is 60-65 ~m (Table 3 and 5) or 50-55 I,m (Table 4 and 6). Drying conditions: 10 days at room temperature.

Before the commenr~ement of we,.~ g, the "coating films" are subjected to defined damage in the form of a parallel cut (i.e. parallel to the longest panel edge) using a Bonder cross-hatch instrument (Model 205; m~nllf~ I u ~ rkPting: Lau, Hemer/(~e~n~ny). The panel edges are protected by applying an edge protector ((~)Icosit 255; m~nnf~ctllrer Inertol AG, Wh~ ul, Swit~erland).

The samples are then subjected to rapid we~th~ring by the salt spray test (DIN 50 021 SS) for 168, 230, 500 and 1200 hours and to a hllmi~ test (ASTM D 4585-87) for 500 hours.
The results are cornpiled in Tables 3 to 11. The results are evaluated based on the relevant DIN standards according to an evaluation key, by in~ ting a corrosion protection factor CPF. The CPF is an additive factor based on ~sses.cment of the coating (film) and an ~.cse.c.cment of visible subfilm corrosion and the appearance of the metal snrf~e, and has a ma~imum value of 12 points. The individual maximum values are 6 points in each case.
The larger the numbers, the better the protection from corrosion.

As a further ~.c.s~.s.cment criterion, after the end of the salt spray test and in accordance with DIN 53 167, the subfilm migration in the wet state (cathodic del~min~tion) along the site of deliberate damage is determined. The lower the level of ~el~min~tion, the more effective the corrosion inhibitor tested. After the end of the humidity test, the wet adhesion of the coating formulations is determined in accordance with DIN 53 151 by applying a cross-hatch with the tape tear-off test. According to DIN 53 151 (Scale from Gt 0 to Gt 5), _ wo 97/01606 PCT/EPs6/02C00 a cross-hatch value of Gt 0 co~esponds to cornpletely intact ~hesion of the coating film, whereas Gt S corresponds to inadequate adhesion.

Table 3: Salt spray test~ 168 hours, coat thicl~ness 60-65 ~lm Compound CPFmCePt~ CPFde.l~min~tion (mm total) 2.0 2.0 4.0 105 0.2 % (105)4.6 4.2 8.8 8 0.5%(105) 5.0 4.2 9.2 6 0.2% (106) 4.6 4.2 8.8 s o.s % (106)5.2 4.2 9.4 5 0.2 % (111)4.8 4.2 9.0 7 O.s % (111)4.6 5.0 9.6 7 0.2 % (113)4.6 4.0 8.6 8 0.5 % (113)5.0 4.2 9.2 7 Table 4: Salt spray test, 168 hours; coat thi~n~s 60-65 llm CPF CPF Cathodic Compound Film Metal CPFdel~min~tion (mm total) 2.8 1.6 4.4 105 0.5 %(123) 5.0 5.0 10.0 4 0.8 % (123)5.0 5.0 10.0 4 0.5 % (124)5.0 4.8 9.8 8 0.5 %(125) S.0 5.0 10.0 4 0.8 % (125)5.0 5.0 10.0 4 W O 97/01606 PcT/~~ 6oo Table 5: Salt spray test, 168 hours; coat thickness 50-55 ~n CPF CPF Cathodic Compound FilmMetal CPF~el~min~tion -- 2.4 2.0 4.4 105 0.2 % (101) 4.8 3.8 8.6 10 0.5 % (101) 3.6 3.8 7.4 12 0.2 % (102) 5.0 5.0 10.0 6 0.8 % (102) 5.0 4.5 9.5 4 0.2 % (103) S.0 4.0 9.0 8 0.8 % (103) 5.0 4-5 9-5 4 0.2 % (104) 3.8 3.6 7.4 20 0.5 % (104) 4.0 3.6 7.6 20 0.2 % (107) 5.0 5.2 10.2 8 0.5 % (107) 5.0 5.0 10.0 6 0.2 % (108) 5.0 4.2 9.2 10 0.5 % (108) 5.0 5.2 10.2 6 0.2 % (1 10) 5.0 4.6 9.6 10 0.5 % (110) 5-0 4.8 9.8 6 0.2 % (111) 5.0 5-0 10.0 8 O.S % (111) 5.2 5.3 10.5 6 0.2 % (114) 5.2 5.4 10.4 10 0.8 % (114) 5.4 5.4 10.8 6 0.2 % (115) 5.2 5.3 10.5 8 0.8 % (115) 5.4 5.0 10.4 4 CA 0222l776 l997-ll-2l W O 97/01606 PcT/~l~5 Table 6: Salt spray test, 230 hours; coat thir~n~s.c 60-65 llm CPF CPF Cathodic Compound Film Metal CPFdPl~min~tiQn (mm total) 2.4 2.0 4.4 105 0.2 % (126) 3.8 4.0 7.8 22 0.2 % (135) 4.8 4.8 9.6 8 TabIe 7: Salt spray test, 500 hours; coat thi~knPss; 60-65 llm CPF CPF Cathodic Compound Film Metal CPF~el~min~ or~

- 2.2 2.0 4.2 lOS
0 5 ~0 (120) 2.6 2.5 5.1 65 0.8 % (120) 4.4 5-0 9-4 22 CA 0222l776 l997-ll-2l WO 97/01606 PCT~EP96/02600 Table 8: Salt spray test, 1200 hours; coat ~hi~ knes~ 60-65 llm CPF CPF Cathodic Compound Film Metal CPF(iel~min~tion -- 2.3 0.6 2.9 105 0.5 % (119) 4.8 4.0 8.8 16 0.8 % (119) 4.8 4.0 8.8 12 0.5 % (121) 4.5 4.0 8.5 20 0.8 % (121) 4.5 4.0 8.5 20 o.s %(126) 4.6 4.0 8.6 20 0.8 % (126) 4.6 4.0 8.6 15 0.5 % (128) 4.3 4.0 8.3 35 0.8 % (128) 4.5 4-0 8.5 20 0.5 % (129) 4.5 4.0 8.5 18 wo 97/~16U6 PCT/EP96/02600 Table 9: hllmi~ity test, 500 hours; coat thi~nP~s 60-65 ~un CPF CPF Wet ~dh~sion Compound Film Metal CPF (C~t value) 3.7 4.0 7.7 5 0.2 % (105) 5.6 5.4 11.0 0-1 0.5 % (105) 5.4 5.6 11.0 0 0.2 % (106) 4.8 5.6 10.4 0 0.2 % (111) 5.0 5.0 10.0 0 0.8 % (111) 4.8 5.4 10.2 0 0.2 % (113) 4.4 5 4 9.8 0-1 Table 10: Humidi~ test, 500 hours; coat thickn~s.C 60-65 ~m CPF CPF Wet a~hesi~n Compound Film Metal CPF (Gt value~

2.6 2,0 4.6 5 o s % (1 19) 5.6 5.7 1 1.3 0 0.8 % (119) 5.4 5.7 11.1 o 0.5 %(121) 5.2 5.0 10.2 0 0.8 %(121) 5.2 5.4 10.6 0 0.5 % (126) 5.6 5.5 11.1 0 0.8 % (126) 5.4 5 4 10.8 0 0,5 % (128) 5.2 5.1 10.3 0 0.8 % (128) 5.4 5 4 10.8 0 0.5 %(129) 5.0 5.6 10.6 o W O 97/01606 PCT~EP96/02600 Table 11: Humidity test, 500 hours; coat thickns~ SO-SS ~m Compound CPF CPF CPF Wet ~lh~.c Film Metal (Gt value) 3.8 3.7 7.5 5 0.2 % (101) 6.0 5.6 11.6 0 0.2 % (102) 6.0 6.0 12.0 ~

0.2 % (103) 6.0 5.8 11.8 ~
0.8 % (103) 6.0 6.0 12.0 0 0.2 % (104) 5.2 5.0 10.2 0.5 % (104) 5,4 4.8 10.2 0 0.2 % (107) 5.2 6.0 1 1.2 0.5 % (107) 5.4 5.8 1 1.2 0 0.2 % (108) 5.4 5.5 10.9 0 0.5 % (108) 6.0 6.0 12.0 0 0.2 % (1 10) 5.5 5.5 1 1.0 0 0.5 % (1 10) 6.0 6.0 12.0 ~
0.2 % (1 1 1)6.0 5.8 1 1.8 ~
0.5 % (1 1 1)6.0 6.0 12.0 0 0.2 % (1 14) 3.8 4.3 8. 1 0 0.8 % (1 14) 4.4 5.5 9.9 0 0.2 % (1 15) 5.6 5.5 1 1. 1 0 0.5 % (1 15) 6.0 6.0 12.0 0 WO 97/01606 PCT~EP96/02600 Example 20: Testing of the novel salts in an acrylic dispersion based on Maincoat HG-54 as corrosion inhibitors.

To prepare the coating composition based on Maincoat HG-54, components 1 to 8 (formulation without corrosion inhibitor) or components 1 to 9 (f~ tion comr~ in,~
the corrosion inhibitors) are employed in the stated sequence (cf. Table 12).

Table 12: Acrylic dispersion based on l\~inco~t HG-54 Composition %
by weight 1) Deionised water 3.10 2) Methylcarbitol a) 5-00 3) Orotan 165 b) 0.82 4) Triton CF 10 C) 0.29 5) Drew Plus TS 4380 d) 0.28 6) Acrysol RM 8 e) 0.60 7) Bayferrox 130Mf) 5.72 8) Millicarb g) 17.40 9) Novel corrosion inhibitor 10) Butyl diglycol 3.67 11) Maincote HG-54 h) 58.70 12) Texanol i) 1.50 13) Dibutyl phth~l~tt~. k) 1.50 14) Sodium nitrite (13.8 % in H2O)I~ 0.80 15) Drew T 4310 m) 0.32 16) Arnmonia solution (25 %) 0.30 Total 100.00 Overall solids content: 47 %; pH: 8 to 8.5; a) (~Methylcarbitol: diethylene glycol mono-CA 0222l776 l997-ll-2l W O 97/01606 PCT~EP96/02600-48-methyl ether (Union Carbide); b) ~)Orotan 165: dispersion auxiliary (Rohm & Haas);c) ~!DTriton CF 10: nonionic wetting agent (Rohm & Haas); d) (9Drew Plus TS 4380:
antifo2m ~Drew Chem. Corp.); e) (~)Acrysol RM 8: nonionic thi~kPner (Rohm & Haas);
fJ (~B~yfe~ 130 M: iron oxide red (Bayer AG); g) ~9Millicarb: calcium carbonate (Omya); h) QMaincote HG-54: acrylic ~liepprsionl 41.5 % in ~eioni7Pd water (Rohm &
Haas); i) ~Texanol: co~lPscPnt (~tm~n Chem. Prod., Inc.); k) dibutyl phth~l~te:
pl~stici7Pr (F~stm~n Chem. Prod., Inc.); 1) sodium nitrite: rust film inhibitor (E luka);
m) 6Drew T 4310: nonionic ~ntifo~m (Drew Chem. Corp.).

Components 1 to 8 and 1 to 9 are dispersed using a high-speed stirrer at 3000 revolutions/minute to a (particle) finP.nPss of <15 ~lm. The result of dispersion of the pigment paste thus obt~ined is ~s~.s.ced by del~ il-g the grin~lomet~r value (ISO 1524).
The quantity employed of the novel corrosion inhihitor.C is based on the overall solids content of the formulation without additive (overall solids content: 47%). Con~l-,e..lly, for ~y~mple, an addition of 0.5 % corrosion inhibit~,r to 100 g of diCppr~cion implies a ~ua~lliLy of 0.235 g. The novel corrosion inhibitor salts can also be prepared in situ by sep~a~ ~d-1i*on of weighed amounts of the respective carboxylic acid of the formula I
and of the co~ ,ponding ~minoCil~np~ of the formula V to the pigment paste. Accordingly, for the in situ preparation of corrosion inhi'r)it~r (103) according to Table 13, for PY~mr)lP~
itis nPc~.sc~ry to employ, .sep~f~t~ly, 0.22 g of lauric acid and 0.25 g of 3-aminopropyl-triethoxysilane to obtain a concentration of 1 % of corrosion inhihit~,r (103).

To complete the preparation of the coating composition, components 10 to 16 as in Table 12 are added in the stated sequence, at a reduced stirring speed (1000 revolutions/minute). Subsequently, the pH of the formulation is checked and if nPcç~c~ry is adjusted prior to application with ammonia solution (25 %) to a pH of from 8 to 8.5.

The coating composition can be applied in undiluted form by airless spraying, brushing or rolling or, after dilution, by conventional spraying. Dilution to tne desired spray viscosity is made by adding butylglycol/water ( 1:1 w/w). In the present example, the coating composition is applied by conventional spraying.

The form~ tion is applied to steel panels (19 times 10.5 cm) of tne Bonder type (cold-rolled degreased steel; manufacturer: ~hemet~ll, Frankfurt am Main, ~Jermz~ny) in a coat thickness which after drying is 45-50 ~n (drying conditions: 10 days at room temperature).

W 0 97101606 PCT~EP96/02600 -49-Before the commencement of we~th.~ring, the "coating films" are ~ubjecL~d to defined damage (70 times 05 mm) in the form of a parallel cut (i.e. parallel to the longest panel edge) using a Bonder cross-hatch instrument (model 205; m~mlfa~ rkPtin~ Lau, 5870 Hemer/Germany). The panel edges are protected by applying an edge ~ ecL
(~)Icosit 255; m~nuf~ctllrer Inertol AG, Wi~ , Swit7Prl~nA).

The s~mrl~s are then subjected to rapid we~thPring in the salt spray test (DIN 50 021 SS) for 168 hours and in a humidity test (ASTM D 4585-87) for 330 hours. The results are com~ .d in Tables 13 to 14. The results are evaluated based on the relevant DIN
standards according to an ev~ tio~ key, by inAic~ting a corrosion protection factor CPF.
The CPF is an additive factor based on an ~sescmPnt of the coating (film) and of the steel and has a maximum value of 12 points. The individual m~ximllm values for the coating (film) and the steel are 6 points. The larger the numbers, the better the protection from corrosion.

As a further a~ce~mPnt criterion, after the end of the salt spray test and in acco iance with DIN 53 167, the sllbfilm mi~r~tion in the wet state (cathodic del~min~tion) is ~el~ in~.d along the site of deliberate d~m~ The lower the degree of del~min~tion, the moreeffective the corrosion inhibitor tested. After the end of the humidity test, the wet ~AhP..cion of the coating form~ tion~ is detPrminP~ in accordance with DIN 53 151 by applying a cross-hatch with the tape tear-off test. According to DIN 53 151 (Scale from Gt 0 to Gt 5), a cross-hatch value of Gt 0 corresponds to a compl~tely intact adhesion of the coating film, whereas Gt S corresponds to inadequate adhesion.

W 0 97/01606 PCT~EPg6/02600 - ~0 -Table 13: Salt spray test, 168 hours; coat thiclrn~.,cc 45-50 ~n Compound CFiPlFMCePtaFl CPFdel~min~ti-)n (mm total) 3.0 3.6 6.6 105 0.5 % (111) 44 5.6 10.0 20 0.8 % (111) 4.4 4.5 9.9 12 1.0 % (103) 4.6 5.2 9.8 14 2.0 % (103) 4.8 5.0 9.8 5 0.22 g lauAc acid 5.0 4.8 9.8 13 0.25 g aminosilanea) 0.45 g lauric acid 5.0 4.6 9.6 7 0.49 g ~mino.~ n~o.a) a) 3-Aminopropyltriethoxysilane (E;luka 09324) 0.22 g of lauric acid and 0.25 g of 3-aminoplo~yll,iethoxysilane correspond to 1.0 ~ of compound (103). 0.45 g of lauric acid and 0.49 g of 3-aminopropyltriethoxysilanecorrespond to 2.0 % of compound (103).

Table 14: Humidity test, 330 hours; coat thickn~ss 45-50 llm CPF CPF Wetadhesion Compound Film Metal CPF (Gt value) - 3.0 0.6 3.6 ) 5 0.5 ~o (111) 3.4 3 5 6.9 5 O.~o(lll) 3.4 4-0 7.4 2 Example 21: Testing of the novel salts in solvent-containing 2-component epoxy resin formulations based on (~'Araldit GZ 7071/HY 815 as corrosion inhibitors.

W O 97101606 PCT/h~-çl~6oo To prepare the coating composition based on ~3;)Araldit GZ 707 l/HY 815, components 1 to 10 (fi~ tion without corrosion inhihitor) or components 1 to 11 (formulation co~t~ining the corrosion inhibitors) are employed in the stated sequence (cf. Table 15).
The quantity employed of the novel corrosion inhi~itQrS is based on the overall solids content of the total formulation without corrosion inhibitor (overall solids content: 64.8%).
Accordingly, for e~m~ r an addition of 0.5 % coIrosion inhibitor to 128.15 g of overall formulation implies a (lu~~ y of 0.41 g.

Table 15: 2 component epoxy/poly~mi(lo~mine primer Composition % by weight Component A:
1) AralditGZ7071(75%inxylene)a) 24.2 2) Aerosil R 972b) 0.5 3) Thixatrol STC) 0.2 4) Kronos RN 56d) 25.0 5) Bayferrox 318 Me) 0.1 6) Talkum AT Extrafl 15.8 7) Blanc Fixeg) 14.2 8) Cyclohexanone 8.3 9) Xylene 11.7 10) n-Butanol 10.0 11) Novelcorrosioninhibitor Total 1 10.0 Component B:
12) Hardener HY 815 (50 % in xylene)h) 18.15 Overall solids content: 64.8 %; a) g~Araldit GZ 7071: epoxy resin (Ciba-Geigy AG);
b) (~Aerosil R 972: hydrophobicized silicic acid, anti-settling/thickP,ning agent (Degussa);

W O 97/01606 PCT~ v2~~

c) ~)Thixatrol ST: thioxtropic agent (NL-~hPmic~lc); d) (g)Kronos RN 56: titanium dioxide (Kronos Titan GmbH); e) ~Bayferrox 318 M: iron oxide black (Bayer AG);
(g)Talhlm AT Extra: Norwegian; g) ~)Blanc Fixe: barium sulfate (S~c-htl~ben); h)~Harter HY 815: poly~mido~mine hardener (Ciba-Geigy AG).

The resulting component A (formnl~ti~n with and without corrosion inhibitor) is di~elsed to a particle finenP~s~c < 15 ~n using a hori7ont~1 ball mill. The result of dispersion is assessed by (i~PI~ g the grindom~ter value (ISO 1524).

To apply the coating composition, 110 g of components A (formulation without anLicollosion additive) or 110 + X g (formulation with corrosion inhibitor) are mixed with 18.15 g of component B and the mixture is applied, after an induction time of 30 mim~t~Psc~
by spraying to steel panels (19 x 10.~ cm) of the Bonder type (cold-rolled degreased steel;
m~nnf~ctllrer ChP,m~t~ll, Frankfurt am Main/Germany) in a coat thi~lrnPs~e which after drying is 50 ~Im. Drying conditions: 10 days at room temperature. AdjustmPnt to the desired spray viscosity is made by dilution with xylene.

Before the commPn~,Pm~nt of we~thPrin~, the "coa~ng films" are subjected to defined damage in the form of parallel cut (i.e. parallel to the longest panel edge) using a Bonder cross-hatch instrument (model 205; m~nllf~Lu~ rkPtin~: Lau, Hemer/~JPrm~ny). Thepanel edges are protected by applying an edge protector (~Icosit 255; m~nllf~ctllrçr ~ertol AG, Winterthur, Swit7P.rl~n(l).

The s~mples are subsequently subjected to rapid we~thPring by the salt spray test (DIN 50 021 SS) for 322 hours. The results are collated in Table 16. The evaluation of the results is made in analogy to Examples 19 and 20.

Table 16: Salt spray test, 322 hours; coat thiçknPss 50 llm CPF CPF Cathodic Compound FilmMetal CPF~P.lslmin~tion (mm total) 4.0 3.8 7.8 37 0.2 % (111) 4.8 4.7 9.~ 13 2.0 % (1 1 1) 4.8 5.2 10.0 1 1 W O 97/01606 PCT~EP96/02600 -53-F.Y~mr le 22: Testing of the novel salts in solvent-co~ 2-component one-coatchassis fini.chPs based on an amine-functional and an epoxy-filnr.tion~l acrylate as corrosion inhibitors.

To prepare the coating composition, components 1 to 7 are employed in the statedsequence (Table 17) and then ~ per.se~l to a fin~ of grind < 15 ~lm on a ho. ;7.on~ ball mill. The result of dispersion is ~sessed by dele~ the grindometer value (ISO 1524).

Table 17: 2-component one-coat finish based on Setalux AA EPL 2514/
Setalux AA EPL 2515 Composition % by weight Component A:
1) Setalux AA EPL 2514 (55 % supply form)a) 26.60 2) Anti Terra 203b) 0.05 3) Bayferrox 3920C) 16.00 4) TaLb~m AT Extrad) 6.00 5) Barium sulfate EWOe) 6.00 ~ 6) BYK 066f) 0.10 7) Butyl acetatlSolvesso lOOg)/ 13 30 metho~yplvpyl acetate = 1:1:1 8) BYK 331h) 0.10 9) BYK 358i) 0.15 10) Butyl acetate/Solvesso lOOg)/
methoxypropyl acetate = 1:1:1 18.30 11) Novel corrosion inhibitor Component B:
12) Setalux AA EPL 2515 (60 % supply form)k) 13.40 Total 100.00 CA 0222l776 l997-ll-2l W O 97/01606 PCT~EP96/02600 -54-Overall solids content: 53.6 9to; a) <~Setalux AA EPL 2514: amine-fnn~tinn~l acrylic resin (Akzo Nobel); b) ~Anti Terra 203: ~ntifloslting agent (BYK-Chemie GmbH); c) (~Bay-felmx 3920: iro~oxi~ yellow (Bayer AG); d) (~DTaLkum AT Extra: Norwegian; e) barium sulfate EWO: Firma Lamberti; f) ~)BYK 066: antifoam (BYK-Chemie GmbH);
g) ~Solvesso 100: mixture of aromatics (Deutsche Exxon ~h~qmic~l GmbH); h) ~)BYK331: levelling ~ssict~nt (BYK-Chemie GmbH); i) ~)BYK 358: levelling ~ t~nt (BYK-Chemie GmbH); k) ~)Setalux AA EPL 2515: epoxy-functional acrylate (Akzo Nobel).

Then components 8, 9 and 10 (fo~mlllation without corrosion inhibitor) or components 8 to 11 (formulation cont~ining the corrosion inhibitors) are added and t'ne mixture is redispersed in order to homogeni~ the paint batch. The quantity of corrosion inhibitor employed is based on tne overall solids content of the coating fnrmnl~tinn (component A
and B). For example, an added quantity of 1 % implies a quantity of 0.536 g relative to 100 g of overall formulation.

For application, the finichpd co~ )ollent A is mixed with component B and the Il~iAlulc; is then applied by spraying to steel panels (19 x 10.5 cm) of the Bonder type (cold-rolled degreased steel; m~nllf~(~t-lrer: (~h~met~ll, Fr~nkfurt am Main/~çrm~ny) in a coat thil~L n~.c which after drying is 45-50 ~Im. Drying conditions: 10 days at room tempe~

Before the com~çn~em~q-nt of we~thering, the "coating films" are subjected to defined damage in the form of a parallel cut (i.e. parallel to the longest panel edge) using a Bonder cross-hatch instrument (model 205; m~nufaclule~ larketing: Lau, Hemer/Germany). The panel edges are protected by applying an edge protector ((~Icosit 255; m~nuf~tllrer Inertol AG, Winterthur, Swit7erl~sncl).

The samples are subsequently subjected to rapid we~thering in a salt spray test (DIN 50 021 SS) for 216 hours. The results are collated in Table 18. The evaluation of the results is made in analogy to Examples 19 and 20.

W O 97/01606 PCT~EP96/02600 Table 18: Salt spray test, 216 hours; coat thic~n~ss 45-50 ~
CPP CPF Cathodic - Compound FilmMetal CPF~ min~tion (mm total) -- 3.2 2.7 5.~ 105 1.4 % (111) 4.0 5.0 9.0 12

Claims

WHAT IS CLAIMED IS:

1. A coating composition comprising a) an organic film-forming binder and b) as corrosion inhibitor .alpha.) at least one salt and/or .beta.) at least one amide derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer, or a carboxylic acid of the formula I

(I) in which R1 is hydrogen, C1-C25alkyl, C2-C25alkyl interrupted by oxygen or sulfur, C2-C24alkenyl, C4-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl;
C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl;
C13-C26polycycloalkyl, C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl; -COR6, a 5- or 6-membered heterocyclic ring which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen or carboxyl; a 5- or 6-membered heterocyclic ring which is benzo-fused and is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen or carboxyl; or else R1 is a radical of the formula II, III
or IV

(II) (III) (IV) R2, R3, R4 and R5 independently of one another are hydrogen, hydroxyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
C10-C12naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; or are -COR6, with the proviso that, if one of the radicals R2, R3, R4 and R5 is hydroxyl, the other radical attached to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and R5, together with the carbon atom to which they are attached, form an unsubstituted or C1-C4alkyl-substituted C5-C12cycloalkylidene ring, R6 is hydroxyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; or is or , R7, R8, R9, R10 and R11 independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C1-C25haloalkyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; C1-C18alkylthio, C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
C10-C12naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; phenoxy or naphthoxy which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkoxy which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl; C10-C12naphthylalkoxy which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; or else the radicals R8 and R9 or the radicals R9 and R10 or the radicals R10 and R11 or the radicals R7 and R11, together with the carbon atoms to which they are attached, form an unsubstituted or C1-C4alkyl-, halogen- or C1-C4alkoxy-substituted benzo ring, with the proviso that at least one of the radicals R7, R8, R9, R10 and R11 is hydrogen, R12 is hydroxyl, halogen, nitro, cyano, CF3, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C1-C25haloalkyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxgyen or sulfur; C1-C18alkylthio or C2-C24alkenyl, R13 and R14 independently of one another are hydrogen, C1-C25alkyl, C1-C18alkoxy or -Y-(CH2)sCOR6, R15 and R16 independently of one another are hydrogen, C1-C25alkyl, C3-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl, X1 is a direct bond, oxygen, sulfur, , C1-C18alkylene, C2-C18alkylene which is interrupted by oxygen or sulfur; C2-C18alkenylene, C2-C18alkynylene, C2-C20alkylidene, C7-C20phenylalkylidene or C5-C8cycloalkylene, with the proviso that, if m and n are 0, X1 is other than oxygen and sulfur, Y is oxygen or , Ra is hydrogen or C1-C8alkyl, m and n independently of one another are integers from 0 to 10, p is an integer from 0 to 4, s is an integer from 1 to 8, and ii) an aminosilane of the formula V

(V) in which R17 and R18 independently of one another are hydrogen, C1-C25alkyl, 2-hydroxyethyl, C3-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl or , R19 is C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; hydroxyl, C1-C18alkoxy or C2-C24alkenyl, R20 is hydroxyl, C1-C18alkoxy or C2-C18alkoxy which is interrupted by oxygen or sulfur;
and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C8alkyl, X2 is C1-C18alkylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, phenylene or naphthylene which is unsubstituted or substituted by C1-C4alkyl; or is C4-C18alkylene which is interrupted by oxygen, sulfur or , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or 2.

2. A coating composition according to claim 1, wherein R1 is C1-C25alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur; C2-C18alkenyl, C5-C12cycloalkyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl;
C5-C12cycloalkenyl which is unsubstituted or substituted C1-C4alkyl and/or carboxyl;
C13-C26polycycloalkyl, C7-C9phenylalkyl, -COR6 or a radical of the formula II, III or IV

(II) (III) (IV) R2, R3, R4 and R5 independently of one another are hydrogen, hydroxyl, C1-C12alkoxy, C2-C12alkoxy which is interrupted by oxygen or sulfur; C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur; C2-C18alkenyl, C5-C12cycloalkyl, C5-C12cycloalkenyl, phenyl, naphthyl, C7-C9phenylalkyl, C10-C12naphthylalkyl or -COR6, with the proviso that, if one of the radicals R2, R3, R4 and R5 is hydroxyl, the other radical attached to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and R5, together with the carbon atom to which they are attached, form a C5-C10cycloalkylidene ring, R6 is hydroxyl, C1-C12alkoxy, C2-C12alkoxy which is interrupted by oxygen or sulfur; or is or , R7, R8, R9, R10 and R11 independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur; C1-C18haloalkyl, C1-C12alkoxy, C2-C12alkoxy which is interrupted by oxygen or sulfur; C1-C12alkylthio, C2-C18alkenyl, C5-C12cycloalkyl, C5-C12cycloalkenyl, phenyl, naphthyl, C7-C9phenylalkyl, C10-C12naphthylalkyl, phenoxy, naphthoxy, C7-C9phenylalkoxy or C10-C12naphthylalkoxy; or else the radicals R8 and R9 or the radicals R9 and R10 or the radicals R10 and R11 or the radicals R7 and R11, together with the carbon atoms to which they are attached, form a benzo ring, with the proviso that at least one of the radicals R7, R8, R9, R10 or R11 and hydrogen, R12 is hydroxyl, chlorine, nitro, cyano, CF3, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur; C1-C18haloalkyl, C1-C12alkoxy, C2-C12alkoxy which is interrupted by oxygen or sulfur; C1-C12alkylthio or C2-C18alkenyl, R13 and R14 independently of one another are hydrogen, C1-C18alkyl, C1-C12alkoxy or -Y-(CH2)5COR6, R15 and R16 independently of one another are hydrogen, C1-C18alkyl, C3-C18alkyl which is interrupted by oxygen or sulfur; C2-C18alkenyl, C5-C12cycloalkyl, phenyl or naphthyl, R17 and R18 independently of one another are hydrogen, C1-C18alkyl, C3-C18alkyl which is interrupted by oxygen or sulfur; or is C2-C18alkenyl, R19 is C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur; hydroxyl, C1-C12alkoxy or C2-C18alkenyl, R20 is hydroxyl, C1-C12alkoxy or C2-C12alkoxy which is interrupted by oxygen or sulfur;
and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C6alkyl, X1 is a direct bond, oxygen, sulfur, , C1-C12alkylene, C2-C12alkylene which is interrupted by oxygen or sulfur; C2-C12alkenylene, C2-C12alkynylene, C2-C16alkylidene, C7-C16phenylalkylidene or C5-C8cycloalkylene, with the proviso that, if m and n are 0, X1 is other than oxygen and sulfur, X2 is C2-C12alkylene, C2-C16alkylidene, C7-C16phenylalkylidene, C5-C8cycloalkylene, phenylene, naphthylene, or C4-C12alkylene which is interrupted by oxygen, sulfur or , with the proviso that never two nitrogen atoms are attached to the same carbon atom, Y is oxygen or , Ra is hydrogen or C1-C6alkyl, m and n independently of one another are integers from 0 to 8, p is an integer from 0 to 2, and s is an integer from 1 to 6.

3. A coating composition according to claim 1, wherein R1 is C1-C25alkyl, C2-C12alkyl which is interrupted by oxygen; C2-C18alkenyl, C5-C12cycloalkyl, C5-C12cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl; C7-C9phenylalkyl, -COR6 or a radical of the formula II or III

(II) (III) R2, R3, R4 and R5 independently of one another are hydrogen, C1-C8alkoxy, C1-C18alkyl, C2-C12alkyl which is interrupted by oxygen; C2-C12alkenyl, C5-C8cycloalkyl, C5-C8cycloalkenyl, phenyl, naphthyl, benzyl or -COR6, or else R2 and R3 or R4 and R5, together withthe carbon atom to which they are attached, form a C5-C7cycloalkylidene ring, R6 is hydroxyl, C1-C12alkoxy, C2-C12alkoxy which is interrupted by oxygen or sulfur; or is or , R7, R8, R9, R10 and R11 independently of one another are hydrogen, hydroxyl, chlorine, nitro, -COR6, C1-C12alkyl, C2-C12alkyl which is interrupted by oxygen; C1-C8alkoxy, C1-C8alkylthio, C2-C12alkenyl, C5-C8cycloalkyl, C5-C8cycloalkenyl, phenyl, naphthyl, benzyl, phenoxy, naphthoxy or benzyloxy; or else the radicals R9 and R10 or the radicals R10 and R11 together with the carbon atoms to which they are attached, form a benzo ring, with the proviso that at least one of the radicals R7, R8, R9, R10 and R11 is hydrogen, R12 is hydroxyl, chlorine, C1-C12alkyl, C1-C12alkoxy, C2-C12alkoxy which is interrupted by oxygen, R15 and R16 independently of one another are hydrogen, C1-C12alkyl, C2-C12alkenyl, C5-C7cycloalkyl, phenyl or naphthyl, X1 is a direct bond, sulfur, , C1-C12alkylene, C2-C12alkylene which is interrupted by oxygen; C2-C12alkenylene or C5-C8cycloalkylene, with the proviso that, if m and n are 0, X1 is other than sulfur, m and n independently of one another are integers from 0 to 8, and p is an integer from 0 to 2.

4. A coating composition according to claim 1, wherein R1 is C1-C25alkyl, C2-C18alkenyl, C5-C8cycloalkyl, C5-C8cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl; benzyl, -COR6 or a radical of the formula II or III

(II) (III) R2, R3, R4 and R5 independently of one another are hydrogen, C1-C12alkyl, C2-C12alkenyl, cyclohexyl, phenyl, naphthyl, benzyl or -COR6, R6 is hydroxyl, C1-C8alkoxy or , R7 is hydrogen, chlorine or C1-C4alkyl, R8 is hydrogen, hydroxyl, C1-C4alkyl, nitro or chlorine, R9 is hydrogen or C1-C4alkyl, R10 is hydrogen, C1-C4alkyl, nitro, chlorine or -COR6, R11 is hydrogen or C1-C4alkyl, R12 is chlorine, C1-C8alkyl or C1-C8alkoxy, R15 and R16 independently of one another are hydrogen or C1-C4alkyl, X1 is a direct bond, sulfur, or C1-C10alkylene, with the proviso that, if m and n are 0, X1 is other than sulfur, m and n independently of one another are integers from 0 to 4, and p is 1.

5. A coating composition according to claim 1, wherein R17 and R18 independently of one another are hydrogen, C1-C12alkyl, C3-C12alkyl which is interrupted by oxygen; or C2-C12alkenyl, R19 is C1-C12alkyl, C3-C12alkyl which is interrupted by oxygen; hydroxyl, C1-C10alkoxy or C2-C12alkenyl, R20 is hydroxyl, C1-C10alkoxy or C2-C10alkoxy which is interrupted by oxygen; and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C4alkyl, X2 is C2-C10alkylene, C2-C12alkylidene, C5-C8cycloalkylene, phenylene, or C4-C12alkylene which is interrupted by , with the proviso that never two nitrogen atoms are attached to the same carbon atom.

6. A coating composition according to claim 1, wherein R17 and R18 independently of one another are hydrogen or C1-C8alkyl, R19 is C1-C8alkyl, hydroxyl, C1-C8alkoxy or C2-C8alkenyl, R20 is hydroxyl or C1-C8alkoxy; and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C4alkyl, X2 is C2-C6alkylene, C5-C8cycloalkylene, phenylene, or C4-C8alkylene which is interrupted by , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1, and b is 0 or 1.

7. A coating composition as claimed in claim 1, wherein R1 is C1-C25alkyl, C2-C16alkenyl, 2-carboxy-4-methylcyclohexenyl, cyclohexyl, benzyl, -COR6 or a radical of the formula II or III

(II) (III) R2, R3, R4 and R5 independently of one another are hydrogen, C1-C8alkyl, phenyl, benzyl or -COR6, R6 is hydroxyl, C1-C4alkoxy or , R7 is hydrogen or C1-C4alkyl, R8 is hydrogen, hydroxyl, C1-C4alkyl, nitro or chlorine, R9 is hydrogen or C1-C4alkyl, R10 is hydrogen, C1-C4alkyl, nitro, chlorine or -COR6, R11 is hydrogen or C1-C4alkyl, R12 is chlorine, C1-C4alkyl or C1-C4alkoxy, R15 and R16 independently of one another are hydrogen or C1-C4alkyl, R17 and R18 independently of one another are hydrogen or C1-C4alkyl, R19 is C1-C6alkyl, C2-C6alkenyl, hydroxyl or C1-C4alkoxy, R20 is hydroxyl or C1-C4alkoxy, and, if a and b togetner are 1, tnree radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C4alkyl, X1 is a direct bond, sulfur, or C1-C10alkylene, with the proviso that, if m and n are O, X1 is other than sulfur, X2 is C2-C6alkylene, cyclohexylene, or C4-C8alkylene which is interrupted by , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1, b is 0 or 1, m and n independently of one another are 0, 1 or 2, and p is 0 or 1.

8. A coating composition according to claim 1, wherein R1 is C1-C18alkyl, 2-carboxy-4-methylcyclohexenyl, -COR6 or a radical of the formula II
or III

(III) (II) R2 is hydrogen, R3 is hydrogen or -COR6, R4 and R5 are hydrogen, R6 is hydroxyl, R7 is hydrogen, R8 is hydrogen, hydroxyl, C1-C4alkyl, nitro or chlorine, R9 is hydrogen, R10 is hydrogen, C1-C4alkyl or nitro, R11 is hydrogen, R17 and R18 are hydrogen or methyl, R19 is C1-C4alkyl, hydroxyl or C1-C4alkoxy, R20 is hydroxyl or C1-C4alkoxy, and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen, X1 is a direct bond, sulfur, or C1-C8alkylene, with the proviso that, if m and n are 0, X1 is other than sulfur, X2 is C2-C4alkylene, or C4-C6alkylene which is interrupted by with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1, b is 0 or 1, m and n independently of one another are 0 or 1, and p is 0.

9. A coating composition according to claim 1, wherein component (.beta.) is derived from an aminosilane of the formula V in which at least one of the radicals R17 and R18 is hydrogen.

10. A coating composition according to claim 1, wherein component (.alpha.) is formed in situ in the preparation of the coating composition by separate addition of components (i) and (ii) and subsequent mixing of the coating composition.

11. A coating composition according to claim 1, which is a surface-coating material.

12. A coating composition according to claim 1, which is an aqueous surface-coating material.

13. A coating composition according to claim 1, wherein component a) is an epoxy resin, a polyurethane resin, a polyester resin, an acrylic resin, an acrylic copolymer resin, a polyvinyl resin, a phenolic resin, an alkyd resin or a mixture of such resins.

14. A coating composition according to claim 1, additionally comprising one or more components from the group consisting of pigments, dyes, fillers, flow control agents, dispersants, thixotropic agents, adhesion promoters, antioxidants, light stabilizers and curing catalysts.

15. A coating composition according to claim 1, wherein component (b) is present in a quantity of from 0.01 to 20 % based on the weight of the overall solids content of the coating composition.

16. A process for preparing a coating composition comprising a salt according to claim 1, which comprises mixing an organic film-forming binder with at least one carboxylic acid of the formula I according to claim 1 and with at least one aminosilane of the formula V
according to claim 1.

17. A salt derived from i) a polyacrylic acid, an acrylic acid-maleic acid copolymer or a carboxylic acid of the formula I

(I) in which R1 is hydrogen, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur;
C2-C24alkenyl, C4-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl and/or carboxyl; C13-C26polycycloalkyl, C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl; -COR6, a 5- or 6-membered heterocyclic ring which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen or carboxyl; a 5- or 6-membered heterocyclic ring which is benzo-fused and is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen or carboxyl; or else R1 is a radical of the formula II, III or IV

(II) (III) (IV) R2, R3, R4 and R5 independently of one another are hydrogen, hydroxyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl;

C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
C10-C12naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; or are -COR6, with the proviso that, if one of the radicals R2, R3, R4 and R5 is hydroxyl, the other radical attached to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and R5, together with the carbon atom to which they are attached, form an unsubstituted or C1-C4alkyl-substituted C5-C12cycloalkylidene ring, R6 is hydroxyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; or is or , R7, R8, R9, R10 and R11 independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C1-C25haloalkyl, C1-C18alkoxy, C2-18alkoxy which is interrupted by oxygen or sulfur; C1-C18alkylthio, C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
C10-C12naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; phenoxy or naphthoxy which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkoxy which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl; C10-C12naphthylalkoxy which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; or else the radicals R8 and R9 or the radicals R9 and R10 or the radicals R10 and R11 or the radicals R7 and R11, together the carbon atoms to which they are attached, form an unsubstituted or C1-C4alkyl-, halogen- or C1-C4alkoxy-substituted benzo ring, with the proviso that at least one of the radicals R7, R8, R9, R10 and R11 is hydrogen, R12 is hydroxyl, halogen, nitro, cyano, CF3, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C1-C25haloalkyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxgyen or sulfur; C1-C18alkylthio or C2-C24alkenyl, R13 and R14 independently of one another are hydrogen, C1-C25alkyl, C1-C18alkoxy or -Y-(CH2)sCOR6, R15 and R16 independently of one another are hydrogen, C1-C25alkyl, C3-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl, X1 is a direct bond, oxygen, sulfur, , C1-C18alkylene, C2-C18alkylene which is interrupted by oxygen or sulfur; C2-C18alkenylene, C2-C18alkynylene, C2-C20alkylidene, C7-C20phenylalkylidene or C5-C8cycloalkylene, with the proviso that, if m and n are 0, X1 is other than oxygen and sulfur, Y is oxygen or , Ra is hydrogen or C1-C8alkyl, m and n independently of one another are integers from 0 to 10, p is an integer from 0 to 4, s is an integer from 1 to 8, and ii) an aminosilane of the formula V

(V) in which R17 and R18 independently of one another are hydrogen, C1-C25alkyl, 2-hydroxyethyl, C3-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl or , R19 is C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; hydroxyl, C1-C18alkoxy or C2-C24alkenyl, R20 is hydroxyl, C1-C18alkoxy or C2-C18alkoxy which is interrupted by oxygen or sulfur;
and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C8alkyl, X2 is C1-C18alkylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, phenylene or naphthylene which is unsubstituted or substituted by C1-C4alkyl; or is C4-C18alkylene which is interrupted by oxygen, sulfur or , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or 2.

18. A salt according to claim 17, derived from i) a carboxylic acid of the formula I in which R1 is hydrogen, C1-C25alkyl, C2-C25alkyl interrupted by oxygen or sulfur; C2-C24alkenyl, C4-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-15cycloalkenyl which is unsubtituted or substituted by C1-C4alkyl; C13-C26polycycloalkyl, C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
-COR6, a 5- or 6-membered heterocyclic ring which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen or carboxyl; a 5- or 6-membered heterocyclic ring which is benzo-fused and is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen or carboxyl; or else R1 is a radical of the formula II, III or IV

(II) (III) (IV) R2, R3, R4 and R5 independently of one another are hydrogen, hydroxyl C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
C10-C12naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; or are -COR6, with the proviso that, if one of the radicals R2, R3, R4 and R5 is hydroxyl, the other radical attached to the same carbon atom is other than hydroxyl; or else R2 and R3 or R4 and R5, together with the carbon atom to which they are attached, form an unsubstituted or C1-C4alkyl-substituted C5-C12cycloalkylidene ring, R6 is hydroxyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; or is or , R7, R8, R9, R10 and R11 independently of one another are hydrogen, hydroxyl, halogen, nitro, cyano, CF3, -COR6, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C1-C25haloalkyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; C1-C18alkylthio, C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C5-C15cycloalkenyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl;
C10-C12naphthylalkyl which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl; phenoxy or naphthoxy which is unsubstituted or substituted by C1-C4alkyl;
C7-C9phenylalkoxy which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl; C10-C12naphthylalkoxy which is unsubstituted or substituted on the naphthyl ring system by C1-C4alkyl, or else the radicals R8 and R9 or the radicals R9 and R10 or the radicals R10 and R11 or the radicals R7 and R11, together the carbon atoms to which they are attached, form an unsubstituted or C1-C4alkyl-, halogen- or C1-C4alkoxy-substituted benzo ring, with the proviso that at least one of the radicals R7, R8, R9, R10 and R11 is hydrogen, R12 is hydroxyl, halogen, nitro, cyano, CF3, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; C1-C25haloalkyl, C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxgyen or sulfur; C1-C18alkylthio or C2-C24alkenyl, R13 and R14 independently of one another are hydrogen, C1-C25alkyl, C1-C18alkoxy or -O-(CH2)sCOR6, R15 and R16 independently of one another are hydrogen, C1-C25alkyl, C3-C25alkyl which is interrupted by oxygen or sulfur; C2-C24alkenyl, C5-C15cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; phenyl or naphthyl which is unsubstituted or substituted by C1-C4alkyl, X1 is a direct bond, oxygen, sulfur, , C1-C18alkylene, C2-C18alkylene which is interrupted by oxygen or sulfur; C2-C18alkenylene, C2-C18alkynylene, C2-C20alkylidene, C7-C20phenylalkylidene or C5-C8cycloalkylene, with the proviso that, if m and n are 0, X1 is other than oxygen and sulfur, m and n independently of one another are integers from 0 to 10, p is an integer from 0 to 4, s is an integer from 1 to 8, and ii) an aminosilane of the formula V in which R17 and R18 independently of one another are hydrogen, C1-C25alkyl, 2-hydroxyethyl, C3-C25alkyl which is interrupted by oxygen or sulfur; or is C2-C24alkenyl or , R19 is C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen or sulfur; or C2-C24alkenyl, R20 is hydroxyl, C1-C18alkoxy or C2-C18alkoxy which is interrupted by oxygen or sulfur;
R21 is hydrogen or C1-C8alkyl, X2 is C1-C18alkylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, phenylene or naphthylene which is unsubstituted or substituted by C1-C4alkyl; or is C4-C18alkylene which is interrupted by oxygen, sulfur or , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or 2.

19. A salt according to claim 17, wherein R1 is C1-C25alkyl, C2-C16alkenyl, 2-carboxy-4-methylcyclohexenyl, cyclohexyl, benzyl, -COR6 or a radical of the formula II or III

(II) (III) R2, R3, R4 and R5 independently of one another are hydrogen, C1-C8alkyl, phenyl, benzyl or -COR6, R6 is hydroxyl, C1-C4alkoxy or , R7 is hydrogen or C1-C4alkyl, R8 is hydrogen, hydroxyl, C1-C4alkyl, nitro or chlorine, R9 is hydrogen or C1-C4alkyl, R10 is hydrogen, C1-C4alkyl, nitro, chlorine or -COR6, R11 is hydrogen or C1-C4alkyl, R12 is chlorine, C1-C4alkyl or C1-C4alkoxy, R15 and R16 independently of one another are hydrogen or C1-C4alkyl, R17 and R18 independently of one another are hydrogen or C1-C4alkyl, R19 is C1-C6alkyl, C2-C6alkenyl, hydroxyl or C1-C4alkoxy, R20 is hydroxyl or C1-C4alkoxy, and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen or C1-C4alkyl, X1 is a direct bond, sulfur, or C1-C10alkylene, with the proviso that, if m and n are 0, X1 is other than sulfur, X2 is C2-C6alkylene, cyclohexylene, or C4-C8alkylene which is interrupted by , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1, b is 0 or 1, m and n independently of one another are 0, 1 or 2, and p is 0 or 1.

20. A salt according to claim 17, wherein R1 is C1-C18alkyl, 2-carboxy-4-methylcyclohexenyl, -COR6 or a radical of the formula II
or III

(II) (III) R2 is hydrogen, R3 is hydrogen or -COR6, R4 and R5 are hydrogen, R6 is hydroxyl, R7 is hydrogen, R8 is hydrogen, hydroxyl, C1-C4alkyl, nitro or chlorine, R9 is hydrogen, R10 is hydrogen, C1-C4alkyl or nitro, R11 is hydrogen, R17 and R18 are hydrogen or methyl, R19 is C1-C4alkyl, hydroxyl or C1-C4alkoxy, R20 is hydroxyl or C1-C4alkoxy, and, if a and b together are 1, three radicals R20 together are N(CH2CH2O-)3, R21 is hydrogen, X1 is a direct bond, sulfur, or C1-C8alkylene, with the proviso that, if m and n are 0, X1 is other than sulfur, X2 is C2-C4alkylene, or C4-C6alkylene which is interrupted by , with the proviso that never two nitrogen atoms are attached to the same carbon atom, a is 1, b is 0 or 1, m and n independently of one another are 0 or 1, and p is 0.

21. A method of protecting a corrodable metal substrate, which comprises applying to this substrate a coating composition according to claim 1 and then drying and/or curing it.

22. Use of a salt or amide defined in claim 1 as a corrosion inhibitor in coating compositions for metallic surfaces.